CN121311114A

CN121311114A - Antifungal composition

Info

Publication number: CN121311114A
Application number: CN202480039774.7A
Authority: CN
Inventors: A·埃德蒙兹; C·C·斯卡伯勒; H·C·沃尔夫; V·格拉索
Original assignee: Syngenta Crop Protection AG Switzerland
Current assignee: Syngenta Crop Protection AG Switzerland
Priority date: 2023-06-14
Filing date: 2024-06-12
Publication date: 2026-01-09
Also published as: WO2024256433A1; AU2024302452A1; AR132946A1; CO2026000206A2; UY40787A; TW202500016A

Abstract

Fungicidal composition comprising a mixture of components (a) and (B), wherein components (a) and (B) are as defined in claim 1, and the use of the composition in agriculture or horticulture for controlling or preventing infestation of plants by phytopathogenic microorganisms, preferably fungi.

Description

Fungicidal compositions

The present invention relates to novel fungicidal compositions, to their use in agriculture or horticulture for controlling diseases caused by phytopathogens, especially phytopathogenic fungi, and to a method of controlling diseases on useful plants.

While many fungicidal compounds and compositions belonging to a variety of different chemical classes have been developed and are being developed for use as fungicides in crops of useful plants, crop tolerance and activity against specific phytopathogenic fungi does not always meet the needs of agricultural practices in many respects. Accordingly, there is a continuing need to find new compounds and compositions having excellent biological properties for controlling or preventing infestation of plants by phytopathogenic fungi. For example, compounds having greater biological activity, a favorable activity profile, increased safety, improved physicochemical properties, increased biodegradability. Or in addition, compositions having a broader spectrum of activity, improved crop tolerance, improved synergistic interaction or enhanced properties, or compositions which exhibit a faster onset or have a longer lasting residual activity or which are capable of reducing the number of applications and/or the rate of application of compounds and compositions required for effective control of phytopathogens, thus enabling beneficial tolerance management practices, reducing environmental impact and reducing operator exposure.

Some of these needs may be addressed using compositions comprising a mixture of different fungicidal compounds having different modes of action (e.g., by combining fungicides having different activity profiles).

According to the present invention there is provided a fungicidal composition comprising as active ingredient a mixture of components (a) and (B), wherein component (a) is a compound of formula (I):

(I)

Wherein the method comprises the steps of

R ¹ is selected from hydrogen, C ₁-C₃ -alkyl, or C ₃-C₆ -cycloalkyl;

R ² is selected from hydrogen, halogen, C ₁-C₃ -alkyl, C ₁-C₄ -haloalkyl, or C ₃-C₆ -cycloalkyl;

R ³ is hydrogen;

R ⁴ is selected from hydrogen or C ₁-C₃ -alkyl;

r ⁵ and R ⁶ are hydrogen;

R ⁷ is selected from hydrogen, C ₁-C₃ -alkyl, C ₁-C₃ -alkylcarbonyl or C ₁-C₃ -alkoxycarbonyl;

Z ¹ is selected from phenyl, or 5-or 6-membered heteroaryl, wherein either of the 5-or 6-membered heteroaryl contains 1, 2, or 3 heteroatoms independently selected from N, O or S, provided that only one is selected from O or S, and wherein either of the phenyl and 5-or 6-membered heteroaryl is unsubstituted or substituted with 1, 2, or 3 substituents independently selected from halogen, cyano, C ₁-C₃ -alkyl, C ₁-C₂ -haloalkyl, or C ₁-C₃ -alkoxy;

X ¹、X² and X ³ are independently selected from CH, N, or S, provided that one of X ¹、X² and X ³ is S, and

A ¹、A² and a ³ are independently selected from CH, N, O, or S, provided that at least one of a ¹、A² and a ³ is selected from N, O or S and no more than one of a ¹、A² and a ³ is O or S;

And

Component (B) is a compound selected from the group consisting of: fluoxazoyl hydroxylamine, benzovindiflupyr, bixafen, fluxapyroxad, isopyrazam, penflufen, penthiopyrad, cyproconazole, fluxapyroxad, fluxad, fluxapyroxad, penflufen boscalid, fluopyram, thiaflufenamid, bixafen, ipflupyraclostrobin, indene picolide, ipratropium, penflufen, fludanazol boscalid, fluopyram, thiaflufenamide, bixafen penoxsulam, indene penoxsulam, ipratropium, penoxsulam, penox, Fluazinam, triphenyltin hydroxide, silthiopham, fenpropimorph, fenpropidin, spiroxamine, cyproconazole, imazalil, boscalid, furfuryl, cyproconazole, difenoconazole, epoxiconazole, flutriafol, hexaconazole, ipconazole, metconazole, myclobutanil, penconazole, propiconazole, tebuconazole, trifloxystrobin, triticonazole, prothioconazole, flupyrad-raz, halofop-butyl, trifluor-oxazole, iprovalicarb, fluquindoxine, metalaxyl-M, cyprodinil, pyrimethanil, kasugamycin, mancozeb, copper fungicides, sulfur, zinc thiazole, captan, folpet, chlorothalonil, dithianon, quinoxyfen, propiconazole, fludioxonil, Iprodione, procymidone, thiabendazole, zoxamide, metrafenone, fluopicolide, propamocarb, fluoethazone, fluoxastrobin sulfonate, alamic acid type benzene-S-methyl, iprovalicarb, cyclophosphamide, cyflufenamid, iso Ding Yiyang quinoline, tetrazolium carbamate, tricyclazole, N-methoxy-N- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] cyclopropanecarboxamide, N, 2-dimethoxy-N- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] propionamide, 1-methoxy-3-methyl-1- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] urea, 1, 3-dimethoxy-1- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] urea, N- [ (1R) -1-benzyl-3-chloro-1-methyl-but-3-enyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-3-chloro-1-methyl-but-3-enyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1R) -1-benzyl-3, 3-trifluoro-1-methyl-propyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-3, 3-trifluoro-1-methyl-propyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl ] -7, 8-difluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-1, 3-dimethyl-butyl ] -7, 8-difluoro-quinoline-3-carboxamide, 8-fluoro-N- [ (1R) -1- [ (3-fluorophenyl) methyl ] -1, 3-dimethyl-butyl ] quinoline-3-carboxamide, 8-fluoro-N- [ (1S) -1- [ (3-fluorophenyl) methyl ] -1, 3-dimethyl-butyl ] quinoline-3-carboxamide, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, N- ((1R) -1-benzyl-3-chloro-1-methyl-but-3-enyl) -8-fluoro-quinoline-3-carboxamide, N- ((1S) -1-benzyl-3-chloro-1-methyl-but-3-enyl) -8-fluoro-quinoline-3-carboxamide, (Z) -3-methoxy-2- [ 2-methyl-5- [4- (trifluoromethyl) triazol-2-yl ] phenoxy ] prop-2-enoic acid methyl ester, (Z) -3-methoxy-2- [ 2-methyl-5- (4-propyltriazol-2-yl) phenoxy ] prop-2-enoic acid methyl ester, (Z) -2- [5- (3-Isopropylpyrazol-1-yl) -2-methyl-phenoxy ] -3-methoxy-prop-2-enoic acid methyl ester, (Z) -3-methoxy-2- [ 2-methyl-5- (3-propylpyrazol-1-yl) phenoxy ] prop-2-enoic acid methyl ester, (Z) -3-methoxy-2- [ 2-methyl-5- [3- (trifluoromethyl) pyrazol-1-yl ] phenoxy ] prop-2-enoic acid methyl ester, (Z) -2- (5-cyclohexyl-2-methyl-phenoxy) -3-methoxy-prop-2-enoic acid methyl ester, (Z) -2- (5-cyclopentyl-2-methyl-phenoxy) -3-methoxy-prop-2-enoic acid methyl ester, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -5-methyl-N-spiro [3.4] oct-3-yl-thiazole-4-carboxamide, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -N-hexyl-5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (2-methoxyacetyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (tetrahydropyran-4-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (oxetane-3-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (tetrahydrofuran-3-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ acetyl- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (2-methylpropanoyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, TAEGRO (i.e., bacillus amyloliquefaciens strain FZB 24), melaleuca alternifolia oil (melaleuca alternifolia extract (commercially available as Timorex Gold, which is a broad spectrum plant biological fungicide)), giant knotweed extract (commercially available as REGALIA), a plant extract based on a lycopodium clavatum extract (commercially available as BOTRISTOP), or aureobasidin a.

The term "compound of formula (I)" refers to component a.

In general, the weight ratio of component (A) to component (B) may preferably be from 100:1 to 1:100, from 50:1 to 1:50, from 20:1 to 1:40, from 15:1 to 1:30, from 12:1 to 1:25, from 10:1 to 1:20, from 5:1 to 1:15, from 3:1 to 1:10, or from 2:1 to 1:5.

Further according to the present invention there is provided a method of controlling or preventing phytopathogenic diseases, notably of phytopathogenic fungi, on useful plants or on their propagation material, which comprises applying the fungicidal composition according to the invention to these useful plants, to their locus or to their propagation material.

The benefits provided by certain fungicidal mixture compositions according to the present invention may also include, inter alia, advantageous levels of biological activity for protecting plants against diseases caused by fungi or superior properties for use as agrochemical active ingredients (e.g., greater biological activity, advantageous activity profile, increased safety, improved physico-chemical properties, or increased biodegradability).

The presence of one or more possible asymmetric carbon atoms in the compound of formula (I) means that the compound can exist in optically isomeric form (i.e. in enantiomeric or diastereoisomeric form). Atropisomers may also be present as a result of limited rotation about a single bond. The present invention includes all those possible isomeric forms (e.g., geometric isomers) and mixtures thereof, for compounds having formula (I). The present invention includes all possible tautomeric forms for the compounds of formula (I) and also includes racemic compounds, i.e. mixtures of at least two enantiomers in a ratio of substantially 50:50.

In each case, the compounds according to the invention having formula (I) are in free form, oxidized form (e.g. N-oxide), or in salt form (e.g. agronomically useful salt form).

The N-oxide is an oxidized form of a tertiary amine or an oxidized form of a nitrogen-containing heteroaromatic compound. For example, A. Albini and S. Pietra are described in 1991 in the publication "Heterocholic N-oxides [ Heterocyclic N-oxides ]", by Boca Raton, CRC Press.

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

As used herein, the term "halogen" or "halo" refers to fluoro (fluoro), chloro (chloro), bromo (bromo), or iodo (iodo), preferably fluoro, chloro, or bromo. This also applies correspondingly to halogens, such as haloalkyl, haloalkenyl, haloalkynyl, haloalkoxy and halocycloalkyl, in combination with other meanings.

As used herein, amino means the —nh ₂ group.

As used herein, cyano means a —cn group.

As used herein, the term "C ₁-C_n -alkyl" refers to a saturated straight or branched hydrocarbon group having 1to n carbon atoms attached via any carbon atom, such as any of the following groups: methyl, ethyl, n-propyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2-dimethylpropyl, 1-ethylpropyl, n-hexyl n-pentyl, 1-dimethylpropyl, 1, 2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl 1, 1-dimethylbutyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 2-dimethylbutyl, 2, 3-dimethylbutyl, 3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1, 2-trimethylpropyl, 1, 2-trimethylpropyl, 1-ethyl-1-methylpropyl, or 1-ethyl-2-methylpropyl.

As used herein, the term "C ₃-C_n -cycloalkyl" refers to tri (3) to n-membered cycloalkyl groups, such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

As used herein, the term "C ₁-C_n -alkoxy" refers to a straight or branched chain saturated alkyl group having one (1) to n carbon atoms (as mentioned above) attached via an oxygen atom, i.e., any of, for example, methoxy, ethoxy, n-propoxy, 1-methylethoxy, n-butoxy, 1-methylpropoxy, 2-methylpropoxy, and 1, 1-dimethylethoxy.

As used herein, the term "C ₁-C_n -haloalkyl" refers to a straight or branched saturated alkyl group (as mentioned above) having from 1 to n carbon atoms attached via any one carbon atom, wherein some or all of the hydrogen atoms of these groups may be replaced with fluorine, chlorine, bromine and/or iodine, i.e., for example, any one of the following: chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl 2-iodoethyl, 2-difluoroethyl, 2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2, 2-difluoroethyl, 2-dichloro-2-fluoroethyl, 2-trichloroethyl, pentafluoroethyl, 2-fluoropropyl 2-iodoethyl, 2-difluoroethyl, 2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2, 2-difluoroethyl 2, 2-dichloro-2-fluoroethyl, 2-trichloroethyl, pentafluoroethyl, 2-fluoropropyl.

As used herein, the term "C ₁-C_n -alkylcarbonyl" refers to a C ₁-C_n -alkyl group attached through a carbon atom of a carbonyl (c=o) group.

As used herein, the term "C ₁-C_n -alkoxycarbonyl" refers to a C ₁-C_n -alkoxy moiety attached through a carbon atom of a carbonyl (or c=o) group.

As used herein, the term "heteroaryl" refers to a 5-or 6-membered aromatic monocyclic group containing 1,2,3, or 4 heteroatoms independently selected from N, O or S. Examples of heteroaryl groups include, but are not limited to, furyl, pyrrolyl, thienyl, pyrazolyl, imidazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl, triazolyl, tetrazolyl, pyrazinyl, pyridazinyl, pyrimidinyl, or pyridyl.

As used herein, the term "control" refers to reducing the number of pests, eliminating pests, and/or preventing further pest damage such that damage to the plant or to plant-derived products is reduced.

As used herein, the term "pest" refers to insects and mollusks present in the storage of agricultural, horticultural, forestry, plant-derived products (such as fruits, grains and wood), as well as those pests associated with the damage of man-made structures. The term pest encompasses all phases of the pest life cycle.

As used herein, the term "effective amount" refers to an amount of a compound or salt thereof that provides a desired effect upon single or multiple applications.

The term "fungicide" as used herein means a compound that controls, alters, or prevents the growth of fungi.

The term "fungicidally effective amount" means the amount of such a compound or combination of such compounds that is capable of affecting fungal growth. The effects of control or alteration include all deviations from natural development, such as killing, retardation, etc., and prevention includes forming a barrier or other defenses within or on the plant to prevent fungal infestation.

The effective amount is readily determined by one skilled in the art using known techniques and by observing results obtained in similar circumstances. In determining the effective amount, many factors are considered, including but not limited to the type of plant or derivative product to be applied, the pest to be controlled and its life cycle, the particular compound being applied, the type of application, and other relevant circumstances.

As used herein, the term "compound having formula (I)" refers to component a, which includes compounds having formula (I) and compounds having formula (I-a).

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

The term "plant propagation material" refers to all reproductive parts of a plant, for example seeds or vegetative parts of a plant such as cuttings and tubers. It includes seeds, in the strict sense, roots, fruits, tubers, bulbs, rhizomes and plant parts.

The term "locus" as used herein means a place where plants grow in or on, or where seeds of cultivated plants are sown, or where seeds are to be placed in soil. It includes soil, seeds, and seedlings, along with established vegetation.

The term "g a.i./ha" as used herein refers to the application rate given in grams of [ g ] of active ingredient [ a.i. ] per unit surface [ ha ]. The unit hectare (symbol ha) is a metric unit equal to the area of a square having a side length of 100 m (1 hm ²) or 10,000 square meters. Hectare is the area unit commonly used in metric systems.

Throughout this document, the expression "composition" represents a different mixture or combination of components (a) and (B) (including the examples defined above), for example in the form of a single "ready-to-use" admixture, in the form of a combined spray mixture (composed of individual formulations of these single active ingredient components) (for example a "tank mix"), and in the combination of these single active ingredients when applied in a sequential manner (i.e. after a suitably short period of time, for example hours or days, one after the other). The order in which components (a) and (B) are administered is not critical to the practice of the present invention.

As used herein, the term "room temperature" or "RT" or "ambient temperature" refers to a temperature of about 15 ℃ to about 35 ℃. For example, rt may refer to a temperature of about 20 ℃ to about 30 ℃.

The following list provides definitions, including preferred definitions, for substituents R¹、R²、R³、R⁴、R⁵、R⁶、R⁷、X¹、X²、X³、A¹、A²、A³ and Z ¹ of the compounds of formula (I) of the present invention. For any of these substituents, any definition given below may be combined with any definition of any other substituent given below or elsewhere in this document.

In one embodiment of the invention, R ¹ is selected from hydrogen, C ₁-C₃ -alkyl, or C ₃-C₆ -cycloalkyl. Preferably, R ¹ is C ₁-C₃ -alkyl or C ₃-C₆ -cycloalkyl. More preferably, R ¹ is methyl, ethyl or cyclopropyl. Even more preferably, R ¹ is methyl.

In one embodiment of the invention, R ² is selected from hydrogen, halogen, C ₁-C₃ -alkyl, C ₁-C₄ -haloalkyl, or C ₃-C₆ -cycloalkyl. Preferably, R ² is hydrogen, halogen, or C ₁-C₃ -alkyl. More preferably, R ² is hydrogen or C ₁-C_3- alkyl. Even more preferably, R ² is hydrogen, methyl, or ethyl. Even more preferably, R ² is hydrogen or methyl.

In one embodiment of the invention, R ³ is hydrogen.

In one embodiment of the invention, R ⁴ is selected from hydrogen or C ₁-C₃ -alkyl. Preferably, R ⁴ is hydrogen, methyl, or ethyl. More preferably, R ⁴ is hydrogen or methyl.

In one embodiment of the invention, R ⁷ is selected from hydrogen, C ₁-C₃ -alkyl, C ₁-C₃ -alkylcarbonyl, or C ₁-C₃ -alkoxycarbonyl. Preferably, R ⁷ is hydrogen, C ₁-C₃ -alkyl, or C ₁-C₃ -alkoxycarbonyl. More preferably, R ⁷ is hydrogen or C ₁-C₃ -alkyl. Even more preferably, R ⁷ is hydrogen, or methyl.

In one embodiment of the invention Z ¹ is selected from phenyl, or 5-or 6-membered heteroaryl, wherein either of said 5-or 6-membered heteroaryl contains 1, 2, or 3 heteroatoms independently selected from N, O or S, provided that only one is selected from O or S, and wherein either of said phenyl and 5-or 6-membered heteroaryl is unsubstituted or substituted with 1, 2, or 3 heteroatoms independently selected from halogen, cyano, C ₁-C₃ -alkyl, A C ₁-C₂ -haloalkyl, or a C ₁-C₃ -alkoxy. Preferably, Z ¹ is phenyl or 6-membered heteroaryl, wherein either of said 6-membered heteroaryl contains 1 or 2 heteroatoms independently selected from N, O or S, provided that only one is selected from O or S, and wherein either of said phenyl and 6-membered heteroaryl is unsubstituted or substituted with 1,2 or 3 heteroatoms independently selected from halogen, cyano, C ₁-C₃ -alkyl, C ₁-C₂ -alkoxy, or a C ₁-C₂ -haloalkyl substituent. More preferably, Z ¹ is phenyl or 6-membered heteroaryl, wherein any of said 6-membered heteroaryl contains 1 heteroatom selected from N, and wherein any of said phenyl and 6-membered heteroaryl is unsubstituted or substituted with 1,2 or 3 groups independently selected from halogen, C ₁-C₃ -alkyl, C ₁-C₂ -alkoxy, or a C ₁-C₂ -haloalkyl substituent. Even more preferably, Z ¹ is phenyl or 6-membered heteroaryl, wherein any of the 6-membered heteroaryl contains 1 heteroatom selected from N, and wherein any of the phenyl and 6-membered heteroaryl is unsubstituted or substituted with 1,2, or 3 substituents independently selected from chloro, fluoro, methyl, methoxy, or trifluoromethyl. Even more preferably still, Z ¹ is selected from phenyl, 2,3, 4-trifluorophenyl, 2, 3-difluorophenyl, 3, 4-difluorophenyl, 2,4, 6-trifluorophenyl, 2, 4-difluorophenyl, 2, 5-difluorophenyl, 3, 5-difluoro-2-pyridinyl, 5-fluoro-2-pyridinyl, 3-fluoro-2-pyridinyl, 2-fluoro-4-methoxy-phenyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 3-methoxyphenyl, 4-fluoro-2-methoxy-phenyl. even more preferably Z ¹ is selected from 2, 4-difluorophenyl, 3, 5-difluoro-2-pyridinyl, 2-fluorophenyl, 4-fluorophenyl or phenyl. Most preferably, Z ¹ is selected from 2, 4-difluorophenyl, 3, 5-difluoro-2-pyridinyl, 2-fluorophenyl, or 4-fluorophenyl.

In one embodiment of the invention, X ¹、X² and X ³ are independently selected from CH, N, or S, provided that no more than one of X ¹、X² and X ³ is S. Preferably, X ¹ is CH or S, X ² is C or N, and X ³ is CH, N, or S, provided that no more than one of X ¹、X² and X ³ is S. More preferably, X ¹ is CH, X ² is CH and X ³ is S, or X ¹ is S, X ² is CH and X ³ is CH, or X ¹ is CH, X ² is N and X ³ is S, or X ¹ is S, X ² is N and X ³ is N.

In one embodiment of the invention, a ¹、A² and a ³ are independently selected from CH, N, O, or S, provided that at least one of a ¹、A² and a ³ is selected from N, O or S, and no more than one of a ¹、A² and a ³ is O or S.

In an embodiment of the present invention, the compound having formula (I) may be a compound having formula (I-a):

(I-A)

Wherein R¹、R²、R³、R⁴、R⁵、R⁶、R⁷、X¹、X²、X³ and Z ¹ are as defined for the compounds according to the invention having formula (I) and a is selected from A1 to a10;

Wherein the alternate lines represent bonds to the C (=o) groups and the arrows represent bonds to the Z ¹ groups.

In another embodiment of the invention, in the compound having formula (I-a), wherein R¹、R²、R³、R⁴、R⁵、R⁶、R⁷、X¹、X²、X³ and Z ¹ are as defined for the compound having formula (I) according to the invention, a is selected from A1, A2, A3, A4, A9, or a10, wherein the staggered lines represent bonds to C (=o) groups and the arrows represent bonds to Z ¹ groups.

In yet another embodiment of the invention, in the compound having formula (I-a), wherein R¹、R²、R³、R⁴、R⁵、R⁶、R⁷、X¹、X²、X³ and Z ¹ are as defined for the compound having formula (I) according to the invention, a is selected from A2, A9, or a10, wherein the staggered lines represent bonds to C (=o) groups and the arrows represent bonds to Z ¹ groups.

In yet another embodiment of the invention, in the compound having formula (I-a), wherein R¹、R²、R³、R⁴、R⁵、R⁶、R⁷、X¹、X²、X³ and Z ¹ are as defined for the compound having formula (I) according to the invention, a is selected from A2 or A9, wherein the staggered lines represent bonds to C (=o) groups and the arrows represent bonds to Z ¹ groups.

Accordingly, the present invention provides compounds of formula (I) having R¹、R²、R³、R⁴、R⁵、R⁶、R⁷、X¹、X²、X³、A¹、A²、A³ and Z ¹ as defined above in all combinations/each permutation. The term "compound of formula (I)" refers to component a.

Further accordingly, the present invention provides compounds of formula (I-a) having R¹、R²、R³、R⁴、R⁵、R⁶、R⁷、X¹、X²、X³、A and Z ¹ as defined above in all combinations/each permutation. The term "compound having formula (I-A)" refers to component A.

In a preferred embodiment of the invention component (A) is a compound of formula (I) wherein R ¹ is selected from C ₁-C₃ -alkyl or C ₃-C₆ -cycloalkyl, R ² is selected from hydrogen or C ₁-C₃ -alkyl, R ³ is hydrogen, R ⁴ is selected from hydrogen or methyl, R ⁵ and R ⁶ are hydrogen, R ⁷ is selected from hydrogen or C ₁-C₃ -alkyl, Z ¹ is selected from 2, 4-difluorophenyl, 3, 5-difluoro-2-pyridinyl, 2-fluorophenyl, Or 4-fluorophenyl, X ¹ is CH, X ² is CH and X ³ is S, or X ¹ is S, X ² is CH and X ³ is CH, or X ¹ is CH, X ² is N and X ³ is S, or X ¹ is S, X ² is N and X ³ is N, and A ¹、A² and A ³ are independently selected from CH, N, O or S, with the proviso that at least one of a ¹、A² and a ³ is selected from N, O or S and no more than one of a ¹、A² and a ³ is O or S, or a salt or N-oxide thereof.

In another preferred embodiment of the invention, component (A) is a compound having the formula (I-A):

(I-A)

Wherein R ¹ is selected from C ₁-C₃ -alkyl or C ₃-C₆ -cycloalkyl, R ² is selected from hydrogen or C ₁-C₃ -alkyl, R ³ is hydrogen, R ⁴ is selected from hydrogen or methyl, R ⁵ and R ⁶ are hydrogen, R ⁷ is selected from hydrogen or C ₁-C₃ -alkyl, Z ¹ is selected from 2, 4-difluorophenyl, 3, 5-difluoro-2-pyridinyl, 2-fluorophenyl, Or 4-fluorophenyl, X ¹ is CH, X ² is CH and X ³ is S, or X ¹ is S, X ² is CH and X ³ is CH, or X ¹ is CH, X ² is N and X ³ is S, or X ¹ is S, X ² is N and X ³ is N, and A is selected from A1, a2, A3, A4, A9 or a10;

Wherein the alternate lines represent bonds to the C (=o) groups and the arrows represent bonds to the Z ¹ groups, or salts or N-oxides thereof.

In another more preferred embodiment of the invention, component (A) is a compound of formula (I-A) wherein R ¹ is selected from C ₁-C₃ -alkyl or C ₃-C₆ -cycloalkyl, R ² is selected from hydrogen or C ₁-C₃ -alkyl, R ³ is hydrogen, R ⁴ is selected from hydrogen or methyl, R ⁵ and R ⁶ are hydrogen, R ⁷ is selected from hydrogen or C ₁-C₃ -alkyl, Z ¹ is selected from 2, 4-difluorophenyl, 3, 5-difluoro-2-pyridinyl, 2-fluorophenyl, Or 4-fluorophenyl, X ¹ is CH, X ² is CH and X ³ is S, or X ¹ is S, X ² is CH and X ³ is CH, or X ¹ is CH, X ² is N and X ³ is S, or X ¹ is S, X ² is N and X ³ is N, and A is selected from A2, a9 or a10;

In another embodiment, component (A) is a compound selected from the group consisting of [5- (2, 4-difluorophenyl) -1,3, 4-thiadiazol-2-yl ] - [ (4R, 7S) -4, 7-dimethyl-4- (1-methylpyrazol-4-yl) -5, 7-dihydrothieno [2,3-c ] pyridin-6-yl ] methanone (X.01); [5- (2, 4-difluorophenyl) isoxazol-3-yl ] - [ rac- (4S, 7R) -4, 7-dimethyl-4- (1-methylpyrazol-4-yl) -5, 7-dihydrothieno [2,3-c ] pyridin-6-yl ] methanone (X.02); [5- (2, 4-difluorophenyl) isoxazol-3-yl ] - [ rac- (4R, 7S) -7-methyl-4- (1-methylpyrazol-4-yl) -5, 7-dihydro-4H-thieno [2,3-c ] pyridin-6-yl ] - [ rac- (4S, 7R) -4-dimethyl-4- (1-methylpyrazol-3-yl) -5, 7-dihydro-6-yl ] - [ rac- (4R, 7S) -4-c ] pyridin-6-yl ] - [ rac- (4-2, 3-difluoro-yl ] - [ rac-3-yl ] - [ rac-4-methyl-6-yl ] - [ 4-methyl ] pyridin-6-yl ] - (X. X.04) - [5- (2, 4-difluorophenyl) -1,3, 4-thiadiazol-2-yl ] - [ 4-methyl-4- (1-methylpyrazol-4-yl) -5, 7-dihydrothieno [2,3-c ] pyridin-6-yl ] methanone (X.05) - [5- (2, 4-difluorophenyl) isoxazol-3-yl ] - [ 4-methyl-4- (1-methylpyrazol-4-yl) -5, 7-dihydrothieno [2,3-c ] pyridin-6-yl ] methanone (X.06) - [5- (2, 4-difluorophenyl) isoxazol-3-yl ] - [ 7-methyl-7- (1-methylpyrazol-4-yl) -4, 6-dihydrothieno [3,2-c ] pyridin-5-yl ] methanone (X.07) - [5- (2, 4-difluorophenyl) isoxazol-3-yl ] - [4- (1-methylpyrazol-4-yl) -5, 7-dihydrothieno [ 4-3-yl ] - [4- (1-methylpyrazol-3-yl) -5-H-2, 4-difluorophenyl ] isoxazol-3-yl ] - [ 4-methyl-4-3-yl ] pyridin-6-yl ] methanone (X.07) - [ 5-yl ] - [5- (1-methyl) 3-methyl ] isoxazol-3-yl ] - [ 4-yl ] methyl ] carbonyl ] methyl-carbonyl 5-yl ] methanone (X.09) [5- (2, 4-difluorophenyl) isoxazol-3-yl ] - [7- (1, 5-dimethylpyrazol-4-yl) -6, 7-dihydro-4H-thieno [3,2-c ] pyridin-5-yl ] methanone (X.10), or [5- (2, 4-difluorophenyl) isoxazol-3-yl ] - [ rac- (4S, 7S) -7- (1, 5-dimethylpyrazol-4-yl) -4-methyl-6, 7-dihydro-4H-thieno [3,2-c ] pyridin-5-yl ] methanone (X.11), or one of its (S) -or (R) -enantiomers, as defined in Table X below.

In another embodiment, component (A) is a compound selected from the group consisting of [5- (2, 4-difluorophenyl) -1,3, 4-thiadiazol-2-yl ] - [ (4R, 7S) -4, 7-dimethyl-4- (1-methylpyrazol-4-yl) -5, 7-dihydrothieno [2,3-c ] pyridin-6-yl ] methanone (X.01); [5- (2, 4-difluorophenyl) isoxazol-3-yl ] - [ rac- (4S, 7R) -4, 7-dimethyl-4- (1-methylpyrazol-4-yl) -5, 7-dihydrothieno [2,3-c ] pyridin-6-yl ] methanone (X.02); [5- (2, 4-difluorophenyl) isoxazol-3-yl ] - [ rac- (4R, 7S) -7-methyl-4- (1-methylpyrazol-4-yl) -5, 7-dihydro-4H-thieno [2,3-c ] pyridin-6-yl ] - [ rac- (4S, 7R) -4-dimethyl-4- (1-methylpyrazol-3-yl) -5, 7-dihydro-6-yl ] - [ rac- (4R, 7S) -4-c ] pyridin-6-yl ] - [ rac- (4-2, 3-difluoro-yl ] - [ rac-3-yl ] - [ rac-4-methyl-6-yl ] - [ 4-methyl ] pyridin-6-yl ] - (X. X.04) - [5- (2, 4-difluorophenyl) -1,3, 4-thiadiazol-2-yl ] - [ 4-methyl-4- (1-methylpyrazol-4-yl) -5, 7-dihydrothieno [2,3-c ] pyridin-6-yl ] methanone (X.05) - [5- (2, 4-difluorophenyl) isoxazol-3-yl ] - [ 4-methyl-4- (1-methylpyrazol-4-yl) -5, 7-dihydrothieno [2,3-c ] pyridin-6-yl ] methanone (X.06) - [5- (2, 4-difluorophenyl) isoxazol-3-yl ] - [ 7-methyl-7- (1-methylpyrazol-4-yl) -4, 6-dihydrothieno [3,2-c ] pyridin-5-yl ] methanone (X.07) - [5- (2, 4-difluorophenyl) isoxazol-3-yl ] - [4- (1-methylpyrazol-4-yl) -5, 7-dihydrothieno [ 4-3-yl ] - [4- (1-methylpyrazol-3-yl) -5-H-2, 4-difluorophenyl ] isoxazol-3-yl ] - [ 4-methyl-4-3-yl ] pyridin-6-yl ] methanone (X.07) - [ 5-yl ] - [5- (1-methyl) 3-methyl ] isoxazol-3-yl ] - [ 4-yl ] methyl ] carbonyl ] methyl-carbonyl 5-yl ] methanone (X.09), or [5- (2, 4-difluorophenyl) isoxazol-3-yl ] - [7- (1, 5-dimethylpyrazol-4-yl) -6, 7-dihydro-4H-thieno [3,2-c ] pyridin-5-yl ] methanone (X.10), or one of its (S) -or (R) -enantiomers, as defined in Table X below.

Table X component (A)

In one embodiment of the invention, component (B) is a compound selected from the group consisting of: fluoxazoyl hydroxylamine, benzovindiflupyr, bixafen, fluxapyroxad, isopyrazam, penflufen, penthiopyrad, cyproconazole, fluxapyroxad, fluxad, fluxapyroxad, penflufen boscalid, fluopyram, thiaflufenamid, bixafen, ipflupyrad, indene picolide, ipratropium, penoxsulam, penox boscalid, fluopyram, thiaflufenamide, bixafen penoxsulam, indene penoxsulam, ipratropium, penoxsulam, penoxsula, Pyridinamide, flumioxazin, fluazinam, triphenyltin hydroxide, silthiopham, fenpropimorph, fenpropidin, spiroxamine, cyproconazole, imazalil, cyproconazole, furfuryl, cyproconazole, difenoconazole, epoxiconazole, flutriafol, hexaconazole, ipconazole, metconazole, myclobutanil, penconazole, propiconazole, tebuconazole, triflumizole, triticonazole, prothioconazole, fluopicolide, penflufen, triflumizole, iprovalicarb, triflumuron, metalaxyl-M, cyprodinil, pyrimethanil, kasugamycin, mancozeb, copper fungicides, sulfur, zinc thiazole, captan, folpet, chlorothalonil, dithianon, quindox, Propionoquinoline, fludioxonil, iprodione, procymidone, thiabendazole, zoxamide, benomyl, fluopyram, propamocarb, fluothiazole pyrithione, trifloxysulfuron, alac acid type benzene-S-methyl, iprovalicarb, phosphorous acid, cyflufenamid, iso Ding Yiyang quinoline, tetrazolium carbamate, tricyclazole, N-methoxy-N- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] cyclopropane-carboxamide, N, 2-dimethoxy-N- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] propionamide, 1-methoxy-3-methyl-1- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] urea, and, 1, 3-dimethoxy-1- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] urea, N- [ (1R) -1-benzyl-3-chloro-1-methyl-but-3-enyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-3-chloro-1-methyl-but-3-enyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1R) -1-benzyl-3, 3-trifluoro-1-methyl-propyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-3, 3-trifluoro-1-methyl-propyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl ] -7, 8-difluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-1, 3-dimethyl-butyl ] -7, 8-difluoro-quinoline-3-carboxamide, 8-fluoro-N- [ (1R) -1- [ (3-fluorophenyl) methyl ] -1, 3-dimethyl-butyl ] quinoline-3-carboxamide, 8-fluoro-N- [ (1S) -1- [ (3-fluorophenyl) methyl ] -1, 3-dimethyl-butyl ] quinoline-3-carboxamide, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, N- ((1R) -1-benzyl-3-chloro-1-methyl-but-3-enyl) -8-fluoro-quinoline-3-carboxamide, N- ((1S) -1-benzyl-3-chloro-1-methyl-but-3-enyl) -8-fluoro-quinoline-3-carboxamide, (Z) -3-methoxy-2- [ 2-methyl-5- [4- (trifluoromethyl) triazol-2-yl ] phenoxy ] prop-2-enoic acid methyl ester, (Z) -3-methoxy-2- [ 2-methyl-5- (4-propyltriazol-2-yl) phenoxy ] prop-2-enoic acid methyl ester, (Z) -2- [5- (3-Isopropylpyrazol-1-yl) -2-methyl-phenoxy ] -3-methoxy-prop-2-enoic acid methyl ester, (Z) -3-methoxy-2- [ 2-methyl-5- (3-propylpyrazol-1-yl) phenoxy ] prop-2-enoic acid methyl ester, (Z) -3-methoxy-2- [ 2-methyl-5- [3- (trifluoromethyl) pyrazol-1-yl ] phenoxy ] prop-2-enoic acid methyl ester, (Z) -2- (5-cyclohexyl-2-methyl-phenoxy) -3-methoxy-prop-2-enoic acid methyl ester, (Z) -2- (5-cyclopentyl-2-methyl-phenoxy) -3-methoxy-prop-2-enoic acid methyl ester (these compounds can be prepared by the methods described in WO 2020/193387), 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -5-methyl-N-spiro [3.4] oct-3-yl-thiazole-4-carboxamide, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -N-hexyl-5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (2-methoxyacetyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (tetrahydropyran-4-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (oxetane-3-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (tetrahydrofuran-3-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ acetyl- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (2-methylpropanoyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, TAEGRO (i.e., bacillus amyloliquefaciens strain FZB 24), melaleuca alternifolia oil (melaleuca alternifolia extract of the tea plant (commercially available as Timorex Gold, which is a broad-spectrum plant biofungstate)), polygonum cuspidatum extract (commercially available as REGALIA), a plant extract based on a lycopodium clavatum extract (commercially available as BOTRISTOP), or aureobasidin a.

In another embodiment of the invention, component (B) is a compound selected from the group consisting of: fluxapyroxad, benzovindiflupyr, bixafen, fluxapyroxad, isopyrazam, penthiopyrad, cyproconazole, boscalid Fluopicolide, thiaflufenamide, bixafen, iprovalicarb, indene picolide, penflufen, trifluoracetam fluopyram, thiaflufenamide, bixafen, ipflupyraclostrobin Inpiramide, penflufen, triflumamid, penflufen, Penoxsulam, triflumizole, iprodione, triflumuron, metalaxyl-M, cyprodinil, pyrimethanil, mancozeb, copper compounds (different salts), sulphur, folpet, chlorothalonil, dithianon, iodoquinazolinone, fludioxonil, metrafenone, fluzopyr-diethyl ketone, trifloxysulphonate, alamic acid-type benzene-S-methyl, phosphorous acid, cyflufenamid, tricyclazole, N-methoxy-N- [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] cyclopropanecarboxamide, N, 2-dimethoxy-N- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] propionamide, 1-methoxy-3-methyl-1- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] urea, 1, 3-dimethoxy-1- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] urea, N- [ (1R) -1-benzyl-3-chloro-1-methyl-but-3-enyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-3-chloro-1-methyl-but-3-enyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1R) -1-benzyl-3, 3-trifluoro-1-methyl-propyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-3, 3-trifluoro-1-methyl-propyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl ] -7, 8-difluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-1, 3-dimethyl-butyl ] -7, 8-difluoro-quinoline-3-carboxamide, 8-fluoro-N- [ (1R) -1- [ (3-fluorophenyl) methyl ] -1, 3-dimethyl-butyl ] quinoline-3-carboxamide, 8-fluoro-N- [ (1S) -1- [ (3-fluorophenyl) methyl ] -1, 3-dimethyl-butyl ] quinoline-3-carboxamide, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, N- ((1R) -1-benzyl-3-chloro-1-methyl-but-3-enyl) -8-fluoro-quinoline-3-carboxamide, N- ((1S) -1-benzyl-3-chloro-1-methyl-but-3-enyl) -8-fluoro-quinoline-3-carboxamide, (Z) -3-methoxy-2- [ 2-methyl-5- [4- (trifluoromethyl) triazol-2-yl ] phenoxy ] prop-2-enoic acid methyl ester, (Z) -3-methoxy-2- [ 2-methyl-5- (4-propyltriazol-2-yl) phenoxy ] prop-2-enoic acid methyl ester, (Z) -2- [5- (3-isopropylpyrazol-1-yl) -2-methyl-phenoxy ] -3-methoxy-prop-2-enoic acid methyl ester, (Z) -3-methoxy-2- [ 2-methyl-5- (3-propylpyrazol-1-yl) phenoxy ] prop-2-enoic acid methyl ester, (Z) -3-methoxy-2- [ 2-methyl-5- [3- (trifluoromethyl) pyrazol-1-yl ] phenoxy ] prop-2-enoic acid methyl ester, (Z) -2- (5-cyclohexyl-2-methyl-phenoxy) -3-methoxy-prop-2-enoic acid methyl ester, (Z) -2- (5-cyclopentyl-2-methyl-phenoxy) -3-methoxy-prop-2-enoic acid methyl ester (these compounds can be prepared by the methods described in WO 2020/193387), 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -5-methyl-N-spiro [3.4] oct-3-yl-thiazole-4-carboxamide, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -N-hexyl-5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (2-methoxyacetyl) amino ] -N- (2, 2-dimethyl-cyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (tetrahydropyran-4-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (oxetane-3-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (tetrahydrofuran-3-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ acetyl- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (2-methylpropionacyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, TAEGRO (i.e., bacillus amyloliquefaciens strain FZB 24), melaleuca alternifolia oil (melaleuca alternifolia extract (commercially available as Timorex Gold, which is a broad-spectrum plant biofungicide)), polygonum cuspidatum extract (commercially available as REGALIA), a plant extract, Plant extracts based on a lycopodium clavatum extract (commercially available as BOTRISTOP), or aureobasidin a.

In another preferred embodiment of the present invention, component (B) is a compound selected from the group consisting of fluxapyroxad hydroxylamine, benzovindiflupyr, azoxystrobin, picolinamide, difenoconazole, prothioconazole, haloxypyrad-zole, cyprodinil, fludioxonil, alaoic acid-benzene-S-methyl, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -5-methyl-N-spiro [3.4] oct-3-yl-thiazole-4-carboxamide, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2, 6-difluoro-4-pyridinyl) - (2-dimethyl-4-carbonyl) -2- [ (2, 6-difluoro-4-pyridinyl) -amino ] -5-methyl-thiazole-4-carboxamide, 2- [ acetyl- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, TAEGRO (i.e., bacillus amyloliquefaciens strain FZB 24), melaleuca alternifolia oil (melaleuca alternifolia extract (commercially available as Timorex Gold, which is a broad spectrum plant biological fungicide)), giant knotweed extract (commercially available as REGALIA), a plant extract based on an askaline wood extract (commercially available as BOTRISTOP), or aureobasidin a.

Still more preferably, component (B) is a compound selected from the group consisting of fluxapyroxad, benzovindiflupyr, azoxystrobin, picolinamide, difenoconazole, prothioconazole, penconazole, cyprodinil, fludioxonil, or an arabinoxylan benzene-S-methyl.

In another embodiment of the present invention, component (B) is a compound selected from the group consisting of fluxapyroxad, benzovindiflupyr, azoxystrobin, picolinamide, difenoconazole, prothioconazole, penflufen, cyprodinil, fludioxonil, or alaac-benzene-S-methyl.

In another embodiment of the invention, component (B) is a compound selected from TAEGRO (i.e., bacillus amyloliquefaciens strain FZB 24), melaleuca alternifolia oil (melaleuca alternifolia extract commercially available as Timorex Gold, which is a broad-spectrum plant biofungicide), giant knotweed extract commercially available as REGALIA, a plant extract based on a Alternaria alternata extract commercially available as BOTRISTOP, or aureobasidin A.

In yet another embodiment of the present invention, component (B) is a compound selected from the group consisting of fluxapyroxad, benzovindiflupyr, azoxystrobin, picolinamide, difenoconazole, prothioconazole, penflufen-zole, cyprodinil, fludioxonil, or alaaci-benzene-S-methyl, TAEGRO (i.e., bacillus amyloliquefaciens strain FZB 24), melaleuca alternifolia oil (melaleuca alternifolia extract of tea plants (commercially available as Timorex Gold, which is a broad-spectrum plant biofungicide)), or aureobasidin A.

These component (B) compounds are mentioned herein and hereinabove by way of the so-called "ISO common name" or another "common name" or trade name used in the individual case. These component (B) compounds are known and are commercially available and/or can be prepared using procedures known in the art and/or reported in the literature.

N-methoxy-N- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] cyclopropanecarboxamide, N, 2-dimethoxy-N- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] propionamide, 1-methoxy-3-methyl-1- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] urea, 1, 3-dimethoxy-1- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] urea, these compounds can be prepared by the methods described in WO 2017/055473, WO 2017/055469, WO 2017/093348 and WO 2017/118689.

Methyl (Z) -3-methoxy-2- [ 2-methyl-5- [4- (trifluoromethyl) triazol-2-yl ] phenoxy ] prop-2-enoate, methyl (Z) -3-methoxy-2- [ 2-methyl-5- (4-propyltriazol-2-yl) phenoxy ] prop-2-enoate, methyl (Z) -2- [5- (3-isopropylpyrazol-1-yl) -2-methyl-phenoxy ] -3-methoxy-prop-2-enoate, methyl (Z) -3-methoxy-2- [ 2-methyl-5- (3-propylpyrazol-1-yl) phenoxy ] prop-2-enoate, methyl (Z) -3-methoxy-2- [ 2-methyl-5- [3- (trifluoromethyl) pyrazol-1-yl ] phenoxy ] prop-2-enoate (these compounds can be prepared by the methods described in WO 2020/079111), methyl (Z) -2- (5-cyclohexyl-2-methyl-phenoxy) -3-methoxy-prop-2-enoate, (Z) -2- (5-cyclopentyl-2-methyl-phenoxy) -3-methoxy-prop-2-enoic acid methyl ester these compounds can be prepared by the methods described in WO 2020/193387.

N- [ (1R) -1-benzyl-3-methyl-but-3-enyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-3-chloro-1-methyl-but-3-enyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1R) -1-benzyl-3, 3-trifluoro-1-methyl-propyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-3, 3-trifluoro-1-methyl-propyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl ] -7, 8-difluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-1, 3-dimethyl-butyl ] -7, 8-difluoro-quinoline-3-carboxamide, 8-fluoro-N- [ (1R) -1- [ (3-fluorophenyl) methyl ] -1, 3-dimethyl-quinoline-3-carboxamide, N- [ (1S) -1-trifluoro-3-methyl-3-butyl ] 3-carboxamide, 8-fluoro-N- [ (1S) -1- [ (3-fluorophenyl) methyl ] -1, 3-dimethyl-butyl ] quinoline-3-carboxamide, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, N- ((1R) -1-benzyl-3-chloro-1-methyl-but-3-enyl) -8-fluoro-quinoline-3-carboxamide, N- ((1S) -1-benzyl-3-chloro-1-methyl-but-3-enyl) -8-fluoro-quinoline-3-carboxamide, these compounds may be prepared by the methods described in WO 2017/153380.

2- [ Cyano- (2, 6-difluoro-4-pyridinyl) amino ] -5-methyl-N-spiro [3.4] oct-3-yl-thiazole-4-carboxamide, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -N-hexyl-5-methyl-thiazole-4-carboxamide, which compounds can be prepared by the methods described in WO 2017207362 A1, WO 2019105933 A1, WO 2020109509 A1, 2- [ (2, 6-difluoro-4-pyridinyl) - (2-methoxyacetyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (tetrahydropyran-4-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (oxetane-3-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (tetrahydrofuran-3-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ acetyl- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (2-methylpropanoyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, these compounds can be prepared from the methods described in WO 2017207362 A1, WO 2019105933 A1, WO 2020109511 A1, WO 20212452 A1.

"TIMOREX Gold ^TM" or "Timorex Gold" as used herein refers to melaleuca alternifolia oil, which is an extract of melaleuca alternifolia of the tea plant, commercially available as Timorex Gold, which is a broad-spectrum plant biological fungicide.

TAEGRO ^TM or TAEGRO ^® as used herein refers to a microbial-based fungicide formulated as a wettable powder containing 130 g/kg of bacillus amyloliquefaciens strain FZB24 (13% w/w, minimum 1 x 10 exp 13 CFU/kg) with accession No. DSM 10271, commercially available as TAEGRO ^®.

As used herein BOTRISTOP cube refers to a broad spectrum biological fungicide, a plant extract based on an extract of lycopodium clavatum

"REGALIA" as used herein refers to a biological fungicide, a plant extract based on giant knotweed extract (commercially available as REGALIA)

Aureobasidin A is an antifungal cyclic ester peptide antibiotic produced by Aureobasidium pullulans (Aureobasidium pullulans). See, e.g., takesako et al J.Antiboot. [ J.antibiotics ]1991, 44, 919-924.WO 2018/102345 discloses the use of aureobasidin a as an agricultural fungicide for the treatment, prevention or control of fungal infections in plants and seeds.

The final compounds, pure in the enantiomeric sense, can be obtained from the racemic starting materials as appropriate via standard physical separation techniques (e.g. reverse phase chiral chromatography) or by stereoselective synthetic techniques (e.g. by using chiral starting materials).

The term "component A" refers to a compound having the formula (I) or a compound having the formula (I-A).

Embodiments according to the present invention are provided, as listed below.

In one embodiment of the present invention, there is provided a fungicidal composition comprising as active ingredient a mixture of components (A) and (B), wherein component (A) is a compound of formula (I) wherein R ¹ is selected from C ₁-C₃ -alkyl or C ₃-C₆ -cycloalkyl, R ² is selected from hydrogen or C ₁-C₃ -alkyl, R ³ is hydrogen, R ⁴ is selected from hydrogen or methyl, R ⁵ and R ⁶ are hydrogen, R ⁷ is selected from hydrogen or C ₁-C₃ -alkyl, Z ¹ is selected from 2, 4-difluorophenyl, 3, 5-difluoro-2-pyridinyl, 2-fluorophenyl, Or 4-fluorophenyl, X ¹ is CH, X ² is CH and X ³ is S, or X ¹ is S, X ² is CH and X ³ is CH, or X ¹ is CH, X ² is N and X ³ is S, or X ¹ is S, X ² is N and X ³ is N, and A ¹、A² and A ³ are independently selected from CH, N, O or S, with the proviso that at least one of A ¹、A² and A ³ is selected from N, O or S and no more than one of A ¹、A² and A ³ is O or S, or a salt or N-oxide thereof, and component (B) is a compound selected from fluxapyroxad hydroxylamine, Benzovindiflupyr, bixafen, fluxapyroxad, isopyrazam, penflufen, penflu penflufen, penthiopyrad, cyproconazole, boscalid, fluopyram, flupyraclostrobin, fluxapyroxad, penflufen, picolide, boscalid penflufen, penthiopyrad, cyproconazole, penflufen boscalid, fluopyram imidazolone, tolfenpyrad, picoxystrobin, pyraclostrobin, famoxadone kresoxim-methyl, trifloxystrobin, azoxystrobin, tetrazolidone, amisulbrom, and other drugs kresoxim-methyl, trifloxystrobin, azoxystrobin tetrazolidone, indazole sulfenamid, metconazole, myclobutanil, penconazole propiconazole, tebuconazole, fluoroether azole metconazole, myclobutanil, penconazole, propiconazole, tebuconazole, epoxiconazole, difenoconazole sterilizing azole, prothioconazole, fluopicolide, penflufen-penconazole, triflumizole, penconazole, penflufen-sodium, iprovalicarb, triflumuron, metalaxyl-M, cyprodinil, pyrimethanil, kasugamycin, mancozeb, copper fungicide, sulfur, zinc thiazole, captan, folpet, chlorothalonil, dithianon, quinoxyfen, propioquinoline, fludioxonil, iprodione, procymidone, thiabendazole, zoxamide, metrafenone, fluopicolide, Propamocarb, fluorothiazolyl ethanone, trifloxysulf, alamic acid type benzene-S-methyl, isothiabendazole, phosphorous acid, cyflufenamid, iso Ding Yiyang quinoline, tetrazolium picolinate, tricyclazole, N-methoxy-N- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] cyclopropanecarboxamide, N, 2-dimethoxy-N- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] propionamide, 1-methoxy-3-methyl-1- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] urea, 1, 3-dimethoxy-1- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] urea, N- [ (1R) -1-benzyl-3-chloro-1-methyl-but-3-enyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-3-chloro-1-methyl-but-3-enyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1R) -1-benzyl-3, 3-trifluoro-1-methyl-propyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-3, 3-trifluoro-1-methyl-propyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl ] -7, 8-difluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-1, 3-dimethyl-butyl ] -7, 8-difluoro-quinoline-3-carboxamide, 8-fluoro-N- [ (1R) -1- [ (3-fluorophenyl) methyl ] -1, 3-dimethyl-butyl ] quinoline-3-carboxamide, 8-fluoro-N- [ (1S) -1- [ (3-fluorophenyl) methyl ] -1, 3-dimethyl-butyl ] quinoline-3-carboxamide, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, N- ((1R) -1-benzyl-3-chloro-1-methyl-but-3-enyl) -8-fluoro-quinoline-3-carboxamide, N- ((1S) -1-benzyl-3-chloro-1-methyl-but-3-enyl) -8-fluoro-quinoline-3-carboxamide, (Z) -3-methoxy-2- [ 2-methyl-5- [4- (trifluoromethyl) triazol-2-yl ] phenoxy ] prop-2-enoic acid methyl ester, (Z) -3-methoxy-2- [ 2-methyl-5- (4-propyltriazol-2-yl) phenoxy ] prop-2-enoic acid methyl ester, (Z) -2- [5- (3-Isopropylpyrazol-1-yl) -2-methyl-phenoxy ] -3-methoxy-prop-2-enoic acid methyl ester, (Z) -3-methoxy-2- [ 2-methyl-5- (3-propylpyrazol-1-yl) phenoxy ] prop-2-enoic acid methyl ester, (Z) -3-methoxy-2- [ 2-methyl-5- [3- (trifluoromethyl) pyrazol-1-yl ] phenoxy ] prop-2-enoic acid methyl ester, (Z) -2- (5-cyclohexyl-2-methyl-phenoxy) -3-methoxy-prop-2-enoic acid methyl ester, (Z) -2- (5-cyclopentyl-2-methyl-phenoxy) -3-methoxy-prop-2-enoic acid methyl ester, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -5-methyl-N-spiro [3.4] oct-3-yl-thiazole-4-carboxamide, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -N-hexyl-5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (2-methoxyacetyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (tetrahydropyran-4-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (oxetane-3-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (tetrahydrofuran-3-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ acetyl- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (2-methylpropanoyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, TAEGRO (i.e., bacillus amyloliquefaciens strain FZB 24), melaleuca alternifolia oil (melaleuca alternifolia extract (commercially available as Timorex Gold, which is a broad spectrum plant biological fungicide)), giant knotweed extract (commercially available as REGALIA), a plant extract based on a lycopodium clavatum extract (commercially available as BOTRISTOP), or aureobasidin a.

In another embodiment of the present invention, there is provided a fungicidal composition comprising as active ingredients a mixture of components (A) and (B), wherein component (A) is a compound of formula (I) wherein R ¹ is selected from C ₁-C₃ -alkyl or C ₃-C₆ -cycloalkyl, R ² is selected from hydrogen or C ₁-C₃ -alkyl, R ³ is hydrogen, R ⁴ is selected from hydrogen or methyl, R ⁵ and R ⁶ are hydrogen, R ⁷ is selected from hydrogen or C ₁-C₃ -alkyl, Z ¹ is selected from 2, 4-difluorophenyl, 3, 5-difluoro-2-pyridinyl, 2-fluorophenyl, Or 4-fluorophenyl, X ¹ is CH, X ² is CH and X ³ is S, or X ¹ is S, X ² is CH and X ³ is CH, or X ¹ is CH, X ² is N and X ³ is S, or X ¹ is S, X ² is N and X ³ is N, and A ¹、A² and A ³ are independently selected from CH, N, O or S, with the proviso that at least one of A ¹、A² and A ³ is selected from N, O or S and no more than one of A ¹、A² and A ³ is O or S, or a salt or N-oxide thereof, and component (B) is a compound selected from fluxapyroxad hydroxylamine, Benzovindiflupyr, bixafen, fluxapyroxad, isopyrazam, penflufen, penflu penthiopyrad, cyproconazole, boscalid, fluopyram, thiaflufenamide, and the like penthiopyrad, cyproconazole, boscalid fluopyram, thiaflufenamide picolide, picolinamide, fluazinam, fenpropidin, cyproconazole, and cyproconazole, difenoconazole, metconazole, penconazole, propiconazole cyproconazole, difenoconazole, metconazole penconazole, propiconazole, mancozeb, copper compounds (different salts), sulfur, folpet, chlorothalonil, dithianon, iodoquinazolinone, fludioxonil, metrafenone, fluorothiazolepezine, trifloxysulf, alamic acid type benzene-S-methyl, phosphorous acid, cyflufenamid, tricyclazole, N-methoxy-N- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] cyclopropanecarboxamide, N, 2-dimethoxy-N- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] propionamide, 1-methoxy-3-methyl-1- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] urea, 1, 3-dimethoxy-1- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] urea, N- [ (1R) -1-benzyl-3-chloro-1-methyl-but-3-enyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-3-chloro-1-methyl-but-3-enyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1R) -1-benzyl-3, 3-trifluoro-1-methyl-propyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-3, 3-trifluoro-1-methyl-propyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl ] -7, 8-difluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-1, 3-dimethyl-butyl ] -7, 8-difluoro-quinoline-3-carboxamide, 8-fluoro-N- [ (1R) -1- [ (3-fluorophenyl) methyl ] -1, 3-dimethyl-butyl ] quinoline-3-carboxamide, 8-fluoro-N- [ (1S) -1- [ (3-fluorophenyl) methyl ] -1, 3-dimethyl-butyl ] quinoline-3-carboxamide, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, N- ((1R) -1-benzyl-3-chloro-1-methyl-but-3-enyl) -8-fluoro-quinoline-3-carboxamide, N- ((1S) -1-benzyl-3-chloro-1-methyl-but-3-enyl) -8-fluoro-quinoline-3-carboxamide, (Z) -3-methoxy-2- [ 2-methyl-5- [4- (trifluoromethyl) triazol-2-yl ] phenoxy ] prop-2-enoic acid methyl ester, (Z) -3-methoxy-2- [ 2-methyl-5- (4-propyltriazol-2-yl) phenoxy ] prop-2-enoic acid methyl ester, (Z) -2- [5- (3-Isopropylpyrazol-1-yl) -2-methyl-phenoxy ] -3-methoxy-prop-2-enoic acid methyl ester, (Z) -3-methoxy-2- [ 2-methyl-5- (3-propylpyrazol-1-yl) phenoxy ] prop-2-enoic acid methyl ester, (Z) -3-methoxy-2- [ 2-methyl-5- [3- (trifluoromethyl) pyrazol-1-yl ] phenoxy ] prop-2-enoic acid methyl ester, (Z) -2- (5-cyclohexyl-2-methyl-phenoxy) -3-methoxy-prop-2-enoic acid methyl ester, (Z) -2- (5-cyclopentyl-2-methyl-phenoxy) -3-methoxy-prop-2-enoic acid methyl ester (these compounds can be prepared by the methods described in WO 2020/193387), 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -5-methyl-N-spiro [3.4] oct-3-yl-thiazole-4-carboxamide, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -N-hexyl-5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (2-methoxyacetyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (tetrahydropyran-4-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (oxetane-3-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (tetrahydrofuran-3-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ acetyl- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (2-methylpropanoyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, TAEGRO (i.e., bacillus amyloliquefaciens strain FZB 24), melaleuca alternifolia oil (melaleuca alternifolia extract of the tea plant (commercially available as Timorex Gold, which is a broad-spectrum plant biofungstate)), polygonum cuspidatum extract (commercially available as REGALIA), a plant extract based on a lycopodium clavatum extract (commercially available as BOTRISTOP), or aureobasidin a.

In yet another embodiment of the present invention there is provided a fungicidal composition comprising as active ingredient a mixture of components (A) and (B), wherein component (A) is a compound of formula (I) wherein R ¹ is selected from C ₁-C₃ -alkyl or C ₃-C₆ -cycloalkyl, R ² is selected from hydrogen or C ₁-C₃ -alkyl, R ³ is hydrogen, R ⁴ is selected from hydrogen or methyl, R ⁵ and R ⁶ are hydrogen, R ⁷ is selected from hydrogen or C ₁-C₃ -alkyl, Z ¹ is selected from 2, 4-difluorophenyl, 3, 5-difluoro-2-pyridinyl, 2-fluorophenyl, Or 4-fluorophenyl, X ¹ is CH, X ² is CH and X ³ is S, or X ¹ is S, X ² is CH and X ³ is CH, or X ¹ is CH, X ² is N and X ³ is S, or X ¹ is S, X ² is N and X ³ is N, and A ¹、A² and A ³ are independently selected from CH, N, O or S, with the proviso that at least one of A ¹、A² and A ³ is selected from N, O or S and no more than one of A ¹、A² and A ³ is O or S, or a salt or N-oxide thereof, and component (B) is a compound selected from fluxapyroxad hydroxylamine, Benzovindiflupyr, azoxystrobin, picolinamide, difenoconazole, prothioconazole, haloxyfop-butyl, cyprodinil, fludioxonil, alamic acid-type benzene-S-methyl, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -5-methyl-N-spiro [3.4] oct-3-yl-thiazole-4-carboxamide, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (tetrahydropyran-4-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ acetyl- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, TAEGRO (i.e., bacillus amyloliquefaciens strain FZB 24), melaleuca alternifolia oil (melaleuca alternifolia extract (commercially available as Timorex Gold, which is a broad-spectrum plant biofungicide)), polygonum cuspidatum extract (commercially available as REGALIA), a plant extract, Plant extracts based on a lycopodium clavatum extract (commercially available as BOTRISTOP), or aureobasidin a.

In another embodiment of the present invention there is provided a fungicidal composition comprising as active ingredient a mixture of components (a) and (B), wherein component (a) is a compound of formula (I) wherein R ¹ is selected from C ₁-C₃ -alkyl or C ₃-C₆ -cycloalkyl, R ² is selected from hydrogen or C ₁-C₃ -alkyl, R ³ is hydrogen, R ⁴ is selected from hydrogen or methyl, R ⁵ and R ⁶ are hydrogen, R ⁷ is selected from hydrogen or C ₁-C₃ -alkyl, Z ¹ is selected from 2, 4-difluorophenyl, 3, 5-difluoro-2-pyridinyl, 2-fluorophenyl, or 4-fluorophenyl;

X ¹ is CH, X ² is CH and X ³ is S, or X ¹ is S, X ² is CH and X ³ is CH, or X ¹ is CH, X ² is N and X ³ is S, or X ¹ is S, X ² is N and X ³ is N, and A ¹、A² and A ³ are independently selected from CH, N, O or S, with the proviso that at least one of A ¹、A² and A ³ is selected from N, O or S and no more than one of A ¹、A² and A ³ is O or S, or a salt or N-oxide thereof, and component (B) is a compound selected from fluxapyroxad hydroxylamine, Benzovindiflupyr, azoxystrobin, picolinamide, difenoconazole, prothioconazole, penconazole, cyprodinil, fludioxonil, or alamic acid-type benzene-S-methyl.

In one embodiment of the present invention, there is provided a fungicidal composition comprising a mixture of components (a) and (B) as active ingredients, wherein component (a) is a compound having the formula (I-a):

(I-A)

Wherein the alternate line represents a bond to a C (=O) group and the arrow represents a bond to a Z ¹ group, or a salt or N-oxide thereof, and component (B) is a compound selected from the group consisting of fluxapyroxad, benzovindiflupyr, bixafen, fluxapyroxad, isopyrazam, penflufen, boscalid, fluopyram, bifidoxamide, ipflupyraclostrobin, picolide, iprovalicarb, penconazole, triflumide, triflumizole, triflumide, penfluxapyroxad, penflufen, fluxapyroxad, penfluxad, penconazole, fluxapyroxad, penciclovir-x, flufen, flupirtine, fluxad-containing a compound such as a salt or an N-oxide thereof, Fluoxastrobin, fenamidone, penconazole, picoxystrobin, pyraclostrobin, and other drugs famoxadone, kresoxim-methyl, trifloxystrobin, azoxystrobin, tetrazolinodone, and the like famoxadone, kresoxim-methyl, trifloxystrobin azoxystrobin, tetrazolidone fenpropidin, spiroxamine, cyproconazole, imazalil, cyproconazole, furfuryl myclobutanil, and cyproconazole, difenoconazole, epoxiconazole, flutriafol, hexaconazole cyproconazole, difenoconazole, epoxiconazole flutriafol, hexaconazole, Triflumizole, iprovalicarb, fluquinline, metalaxyl-M, cyprodinil, pyrimethanil, kasugamycin, mancozeb, copper fungicide, sulfur, zinc thiazole, captan, folpet, chlorothalonil, dithianon, quinoxyfen, propioquinoline, fludioxonil, iprodione, procymidone, thiabendazole, zoxamide, metrafenone, fluopicolide, propamocarb, fluzoxamide, fluoxazamate, alac benzene-S-methyl, isothiabendazole, phosphorous acid, cyflufenamide, isoquinoline Ding Yiyang quinoline, tetrazole picoline, tricyclazole, N-methoxy-N- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] cyclopropane-carboxamide, N, 2-dimethoxy-N- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] propionamide, 1-methoxy-3-methyl-1- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] urea, 1, 3-dimethoxy-1- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] urea, N- [ (1R) -1-benzyl-3-chloro-1-methyl-but-3-enyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-3-chloro-1-methyl-but-3-enyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1R) -1-benzyl-3, 3-trifluoro-1-methyl-propyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-3, 3-trifluoro-1-methyl-propyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl ] -7, 8-difluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-1, 3-dimethyl-butyl ] -7, 8-difluoro-quinoline-3-carboxamide, 8-fluoro-N- [ (1R) -1- [ (3-fluorophenyl) methyl ] -1, 3-dimethyl-butyl ] quinoline-3-carboxamide, 8-fluoro-N- [ (1S) -1- [ (3-fluorophenyl) methyl ] -1, 3-dimethyl-butyl ] quinoline-3-carboxamide, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, N- ((1R) -1-benzyl-3-chloro-1-methyl-but-3-enyl) -8-fluoro-quinoline-3-carboxamide, N- ((1S) -1-benzyl-3-chloro-1-methyl-but-3-enyl) -8-fluoro-quinoline-3-carboxamide, Methyl (Z) -3-methoxy-2- [ 2-methyl-5- [4- (trifluoromethyl) triazol-2-yl ] phenoxy ] prop-2-enoate, (Z) -methyl (Z) -3-methoxy-2- [ 2-methyl-5- (4-propyltriazol-2-yl) phenoxy ] prop-2-enoate, (Z) -methyl (Z) -2- [5- (3-isopropylpyrazol-1-yl) -2-methyl-phenoxy ] -3-methoxy-prop-2-enoate, (Z) -methyl (Z) -3-methoxy-2- [ 2-methyl-5- (3-propylpyrazol-1-yl) phenoxy ] prop-2-enoate, (Z) -methyl (Z) -3-methoxy-2- [ 2-methyl-5- [3- (trifluoromethyl) pyrazol-1-yl ] phenoxy ] prop-2-enoate, (Z) -2- (5-cyclohexyl-2-methyl-phenoxy) -3-methoxy-prop-2-enoic acid methyl ester, (Z) -2- (5-cyclopentyl-2-methyl-phenoxy) -3-methoxy-prop-2-enoic acid methyl ester, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -5-methyl-N-spiro [3.4] oct-3-yl-thiazole-4-carboxamide, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -N-hexyl-5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (2-methoxyacetyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (tetrahydropyran-4-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (oxetane-3-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (tetrahydrofuran-3-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ acetyl- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (2-methylpropionacyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, TAEGRO (i.e., bacillus amyloliquefaciens strain FZB 24), melaleuca alternifolia oil (melaleuca alternifolia extract (commercially available as Timorex Gold, which is a broad-spectrum plant biofungicide)), polygonum cuspidatum extract (commercially available as REGALIA), a plant extract, plant extracts based on a lycopodium clavatum extract (commercially available as BOTRISTOP), and aureobasidin a.

In another embodiment of the present invention, there is provided a fungicidal composition comprising as active ingredient a mixture of components (a) and (B), wherein component (a) is a compound having formula (I-a), wherein R ¹ is selected from C ₁-C₃ -alkyl or C ₃-C₆ -cycloalkyl, R ² is selected from hydrogen or C ₁-C₃ -alkyl, R ³ is hydrogen, R ⁴ is selected from hydrogen or methyl, R ⁵ and R ⁶ are hydrogen, R ⁷ is selected from hydrogen or C ₁-C₃ -alkyl, Z ¹ is selected from 2, 4-difluorophenyl, 3, 5-difluoro-2-pyridinyl, 2-fluorophenyl, or 4-fluorophenyl;

X ¹ is CH, X ² is CH and X ³ is S, or X ¹ is S, X ² is CH and X ³ is CH, or X ¹ is CH, X ² is N and X ³ is S, or X ¹ is S, X ² is N and X ³ is N, and A is selected from A1, A2, A3, A4, A9 or A10;

Wherein the alternate line represents a bond to a C (=O) group and the arrow represents a bond to a Z ¹ group, or a salt or N-oxide thereof, and component (B) is a compound selected from the group consisting of fluxapyroxad hydroxylamine, benzovindiflupyr, bixafen, fluxapyroxad, isopyrazam, penthiopyrad, penflufen, boscalid, fluopyram, bixafen, ipflupyrad, indenopyrazolam, fluindenonamine, triflumidine, pyraclostrobin, trifloxystrobin, Azoxystrobin, tetrazolone, picolide, picolinamide, fluazinam, fenpropidin, fenhexamid, cyproconazole, difenoconazole, metconazole, penconazole, propiconazole, tebuconazole, difenoconazole, prothioconazole, penflufen-oxazole, iprovalicarb, fluquindoxine, metalaxyl-M, cyprodinil, pyrimethanil, mancozeb, copper compounds (different salts), sulfur, folpet, chlorothalonil, dithianon, ioxazinone, fludioxonil, metrafenone, fluorothiazolepyrazinone, trifloxysulf, alamic benzene-S-methyl, phosphorous acid, cyflufenamid, tricyclazole, N-methoxy-N [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] cyclopropanecarboxamide, N, 2-dimethoxy-N- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] propionamide, 1-methoxy-3-methyl-1- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] urea, 1, 3-dimethoxy-1- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] urea, N- [ (1R) -1-benzyl-3-chloro-1-methyl-but-3-enyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-3-chloro-1-methyl-but-3-enyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1R) -1-benzyl-3, 3-trifluoro-1-methyl-propyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-3, 3-trifluoro-1-methyl-propyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl ] -7, 8-difluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-1, 3-dimethyl-butyl ] -7, 8-difluoro-quinoline-3-carboxamide, 8-fluoro-N- [ (1R) -1- [ (3-fluorophenyl) methyl ] -1, 3-dimethyl-butyl ] quinoline-3-carboxamide, 8-fluoro-N- [ (1S) -1- [ (3-fluorophenyl) methyl ] -1, 3-dimethyl-butyl ] quinoline-3-carboxamide, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, N- ((1R) -1-benzyl-3-chloro-1-methyl-but-3-enyl) -8-fluoro-quinoline-3-carboxamide, N- ((1S) -1-benzyl-3-chloro-1-methyl-but-3-enyl) -8-fluoro-quinoline-3-carboxamide, Methyl (Z) -3-methoxy-2- [ 2-methyl-5- [4- (trifluoromethyl) triazol-2-yl ] phenoxy ] prop-2-enoate, (Z) -methyl (Z) -3-methoxy-2- [ 2-methyl-5- (4-propyltriazol-2-yl) phenoxy ] prop-2-enoate, (Z) -methyl (Z) -2- [5- (3-isopropylpyrazol-1-yl) -2-methyl-phenoxy ] -3-methoxy-prop-2-enoate, (Z) -methyl (Z) -3-methoxy-2- [ 2-methyl-5- (3-propylpyrazol-1-yl) phenoxy ] prop-2-enoate, (Z) -methyl (Z) -3-methoxy-2- [ 2-methyl-5- [3- (trifluoromethyl) pyrazol-1-yl ] phenoxy ] prop-2-enoate, (Z) -2- (5-cyclohexyl-2-methyl-phenoxy) -3-methoxy-prop-2-enoic acid methyl ester, (Z) -2- (5-cyclopentyl-2-methyl-phenoxy) -3-methoxy-prop-2-enoic acid methyl ester (these compounds may be prepared by the methods described in WO 2020/193387), 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -5-methyl-N-spiro [3.4] oct-3-yl-thiazole-4-carboxamide, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -N-hexyl-5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (2-methoxyacetyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (tetrahydropyran-4-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (oxetane-3-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (tetrahydrofuran-3-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ acetyl- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (2-methylpropyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, TAEGRO (i.e., bacillus amyloliquefaciens strain FZB 24), Melaleuca alternifolia oil (melaleuca alternifolia extract of tea plant (commercially available as Timorex Gold, which is a broad-spectrum plant biological fungicide)), polygonum cuspidatum extract (commercially available as REGALIA), a plant extract based on a lycopodium clavatum extract (commercially available as BOTRISTOP), or aureobasidin a.

In yet another embodiment of the present invention there is provided a fungicidal composition comprising as active ingredient a mixture of components (a) and (B), wherein component (a) is a compound having formula (I-a), wherein R ¹ is selected from C ₁-C₃ -alkyl or C ₃-C₆ -cycloalkyl, R ² is selected from hydrogen or C ₁-C₃ -alkyl, R ³ is hydrogen, R ⁴ is selected from hydrogen or methyl, R ⁵ and R ⁶ are hydrogen, R ⁷ is selected from hydrogen or C ₁-C₃ -alkyl, Z ¹ is selected from 2, 4-difluorophenyl, 3, 5-difluoro-2-pyridinyl, 2-fluorophenyl, or 4-fluorophenyl;

Wherein the alternate line represents a bond to a C (=O) group and the arrow represents a bond to a Z ¹ group, or a salt or N-oxide thereof, and component (B) is a compound selected from the group consisting of fluxapyroxad hydroxylamine, benzovindiflupyr, azoxystrobin, picolinamide, difenoconazole, prothioconazole, haloxypyr-zole, cyprodinil, fludioxonil, an araac-type benzene-S-methyl, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -5-methyl-N-spiro [3.4] oct-3-yl-thiazole-4-carboxamide, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethyl-butyl) -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -2-methyl-4-carboxamide, and 2- [ cyano ] -N- (2, 6-difluoro-4-pyridinyl) methyl-4-carbonyl ] -4-methyl-3-methyl-carbonyl 2- [ acetyl- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, TAEGRO (i.e., bacillus amyloliquefaciens strain FZB 24), melaleuca alternifolia oil (melaleuca alternifolia extract (commercially available as Timorex Gold, which is a broad spectrum plant biological fungicide)), giant knotweed extract (commercially available as REGALIA), a plant extract based on an askaline wood extract (commercially available as BOTRISTOP), or aureobasidin a.

Wherein the alternate lines represent bonds to the C (=o) group and the arrows represent bonds to the Z ¹ group, or a salt or N-oxide thereof, and component (B) is a compound selected from fluxapyroxad, benzovindiflupyr, azoxystrobin, picolinamide, difenoconazole, prothioconazole, penflufen, cyprodinil, fludioxonil, or alamic acid-type benzene-S-methyl.

Component (A), wherein component (A) is a compound of formula (I), and component (B), are preferred as active ingredients (wherein the term "AX" means a component (A) selected from the group consisting of a compound of formula (I), (I-A) or a compound selected from the group consisting of (X.01), (X.02), (X.03), (X.04), (X.05), (X.06), (X.07), (X.08), (X.09), (X.10), or (X.11), listed in Table X according to the invention as fluxapyroxad hydroxylamine+AX, benzovindiflupyr+AX, bixafen+AX, fluxapyroxad+AX isopyrazam+AX, penflufen+AX isopyrazam+AX penflufen+AX bipyramid+AX, ipflupyraclostrobin+AX Inpiramide+AX, ipratropium+AX Inpiramide+AX Isothiazolin+AX, picoxystrobin+AX, pyraclostrobin+AX, famoxadone+AX kresoxim-methyl+AX, trifloxystrobin+AX kresoxim-methyl+AX trifloxystrobin + AX picolinamide+AX, flumetsulam+AX fluazinam+AX, triphenyltin hydroxide+AX fluazinam+AX triphenyltin hydroxide+AX, imazalil+AX, boscalid+AX, furfuryl azole+AX cyproconazole+AX, difenoconazole+AX, epoxiconazole cyproconazole+AX, difenoconazole+AX epoxiconazole (F-C) propiconazole+AX, tebuconazole+AX, fluoroether azole+AX sterilizing azole+AX, prothioconazole+AX, fluopicolide+AX sterilizing azole+AX, prothioconazole+AX fluopicolide +AX, metalaxyl-M+AX, cyprodinil+AX, pyrimethanil+AX kasugamycin+AX, mancozeb+AX kasugamycin + AX mancozeb+AX dithianon+AX, quinoxylin+AX, propioquinoline+AX fludioxonil+AX, iprodione+AX, procymidone+AX fludioxonil + AX, iprodione + AX Pythiaside+AX, Fluozopiridon+AX, trifloxysulf+AX, alamic acid type benzene-S-methyl+AX, isothiabendamine+AX, phosphorous acid+AX, cyclophosphamide+AX, iso Ding Yiyang quinoline+AX, tetrazolium+AX, tricyclazole+AX, N-methoxy-N- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] cyclopropanecarboxamide+AX, N, 2-dimethoxy-N- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] propionamide+AX, 1-methoxy-3-methyl-1- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] urea +ax, 1, 3-dimethoxy-1- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] urea +ax, N- [ (1R) -1-benzyl-3-chloro-1-methyl-but-3-enyl ] -8-fluoro-quinoline-3-carboxamide +ax, N- [ (1S) -1-benzyl-3-chloro-1-methyl-but-3-enyl ] -8-fluoro-quinoline-3-carboxamide +ax, N- [ (1R) -1-benzyl-3, 3-trifluoro-1-methyl-propyl ] -8-fluoro-quinoline-3-carboxamide +AX, N- [ (1S) -1-benzyl-3, 3-trifluoro-1-methyl-propyl ] -8-fluoro-quinoline-3-carboxamide +AX, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl ] -7, 8-difluoro-quinoline-3-carboxamide +AX, N- [ (1S) -1-benzyl-1, 3-dimethyl-butyl ] -7, 8-difluoro-quinoline-3-carboxamide +AX, 8-fluoro-N- [ (1R) -1- [ (3-fluorophenyl) methyl ] -1, 3-dimethyl-butyl ] quinoline-3-carboxamide +AX, N-fluoro-N- [ (1R) -1- [ (3-fluorophenyl) methyl ] -1, 3-dimethyl-butyl ], 8-fluoro-N- [ (1S) -1- [ (3-fluorophenyl) methyl ] -1, 3-dimethyl-butyl ] quinoline-3-carboxamide +AX, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide +AX, N- [ (1S) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide +AX, N- ((1R) -1-benzyl-3-chloro-1-methyl-but-3-enyl) -8-fluoro-quinoline-3-carboxamide +AX, N- ((1S) -1-benzyl-3-chloro-1-methyl-but-3-enyl) -8-fluoro-quinoline-3-carboxamide +AX, Methyl (Z) -3-methoxy-2- [ 2-methyl-5- [4- (trifluoromethyl) triazol-2-yl ] phenoxy ] prop-2-enoate +AX, (Z) -3-methoxy-2- [ 2-methyl-5- (4-propyltriazol-2-yl) phenoxy ] prop-2-enoate +AX, (Z) -2- [5- (3-isopropylpyrazol-1-yl) -2-methyl-phenoxy ] -3-methoxy-prop-2-enoate +AX, (Z) -3-methoxy-2- [ 2-methyl-5- (3-propylpyrazol-1-yl) phenoxy ] prop-2-enoate +AX, Methyl (Z) -3-methoxy-2- [ 2-methyl-5- [3- (trifluoromethyl) pyrazol-1-yl ] phenoxy ] prop-2-enoate+ax, (Z) -2- (5-cyclohexyl-2-methyl-phenoxy) -3-methoxy-prop-2-enoate+ax, (Z) -2- (5-cyclopentyl-2-methyl-phenoxy) -3-methoxy-prop-2-enoate+ax, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -5-methyl-N-spiro [3.4] oct-3-yl-thiazole-4-carboxamide+ax, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide+ax, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -N-hexyl-5-methyl-thiazole-4-carboxamide +ax, 2- [ (2, 6-difluoro-4-pyridinyl) - (2-methoxyacetyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide +ax, 2- [ (2, 6-difluoro-4-pyridinyl) - (tetrahydropyran-4-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide +ax, 2- [ (2, 6-difluoro-4-pyridinyl) - (oxetane-3-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide +ax, 2- [ (2, 6-difluoro-4-pyridinyl) - (tetrahydrofuran-3-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide +AX, 2- [ acetyl- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide +AX, 2- [ (2, 6-difluoro-4-pyridinyl) - (2-methylpropanoyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide +AX, TAEGRO (i.e., bacillus amyloliquefaciens strain FZB 24) +AX, Melaleuca alternifolia oil (melaleuca alternifolia extract (commercially available as Timorex Gold. RTM., which is a broad-spectrum plant biofungstate)) +AX, giant knotweed extract (commercially available as REGALIA) +AX, a plant extract based on a lycopodium clavatum extract (commercially available as BOTRISTOP) +AX and aureobasidin A+AX.

In another embodiment of the present invention, a mixture of component (A), wherein component (A) is a compound of formula (I), with component (B) is preferred as active ingredient (wherein the term "AX" means a component (A) selected from the group consisting of a compound of formula (I), (I-A) or a compound selected from the group consisting of (X.01), (X.02), (X.03), (X.04), (X.05), (X.06), (X.07), (X.08), (X.09), (X.10), or (X.11), listed in Table X according to the present invention: fluxapyroxad hydroxylamine+AX benzovindiflupyr+AX, bixafen+AX, fluxapyroxad+AX isopyrazam+AX, penflufen+AX isopyrazam+AX penflufen+AX bipyramid+AX, ipflupyraclostrobin+AX Inpiramide+AX, ipratropium+AX Inpiramide+AX Isothiazolin+AX, picoxystrobin+AX, pyraclostrobin+AX, famoxadone+AX kresoxim-methyl+AX, trifloxystrobin+AX kresoxim-methyl+AX trifloxystrobin + AX picolinamide+AX, flumetsulam+AX fluazinam+AX, triphenyltin hydroxide+AX fluazinam+AX triphenyltin hydroxide+AX, imazalil+AX, boscalid+AX, furfuryl azole+AX cyproconazole+AX, difenoconazole+AX, epoxiconazole cyproconazole+AX, difenoconazole+AX epoxiconazole (F-C) propiconazole+AX, tebuconazole+AX, fluoroether azole+AX sterilizing azole+AX, prothioconazole+AX, fluopicolide+AX sterilizing azole+AX, prothioconazole+AX fluopicolide +AX, metalaxyl-M+AX, cyprodinil+AX, pyrimethanil+AX kasugamycin+AX, mancozeb+AX kasugamycin + AX mancozeb+AX dithianon+AX, quinoxylin+AX, propioquinoline+AX fludioxonil+AX, iprodione+AX, procymidone+AX fludioxonil + AX, iprodione + AX Pythiaside+AX, Fluozopiridon+AX, trifloxysulf+AX, alamic acid type benzene-S-methyl+AX, isothiabendamine+AX, phosphorous acid+AX, cyclophosphamide+AX, iso Ding Yiyang quinoline+AX, tetrazolium+AX, tricyclazole+AX, N-methoxy-N- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] cyclopropanecarboxamide+AX, N, 2-dimethoxy-N- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] propionamide+AX, 1-methoxy-3-methyl-1- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] urea +ax, 1, 3-dimethoxy-1- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] urea +ax, N- [ (1R) -1-benzyl-3-chloro-1-methyl-but-3-enyl ] -8-fluoro-quinoline-3-carboxamide +ax, N- [ (1S) -1-benzyl-3-chloro-1-methyl-but-3-enyl ] -8-fluoro-quinoline-3-carboxamide +ax, N- [ (1R) -1-benzyl-3, 3-trifluoro-1-methyl-propyl ] -8-fluoro-quinoline-3-carboxamide +AX, N- [ (1S) -1-benzyl-3, 3-trifluoro-1-methyl-propyl ] -8-fluoro-quinoline-3-carboxamide +AX, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl ] -7, 8-difluoro-quinoline-3-carboxamide +AX, N- [ (1S) -1-benzyl-1, 3-dimethyl-butyl ] -7, 8-difluoro-quinoline-3-carboxamide +AX, 8-fluoro-N- [ (1R) -1- [ (3-fluorophenyl) methyl ] -1, 3-dimethyl-butyl ] quinoline-3-carboxamide +AX, N-fluoro-N- [ (1R) -1- [ (3-fluorophenyl) methyl ] -1, 3-dimethyl-butyl ], 8-fluoro-N- [ (1S) -1- [ (3-fluorophenyl) methyl ] -1, 3-dimethyl-butyl ] quinoline-3-carboxamide +AX, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide +AX, N- [ (1S) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide +AX, N- ((1R) -1-benzyl-3-chloro-1-methyl-but-3-enyl) -8-fluoro-quinoline-3-carboxamide +AX, N- ((1S) -1-benzyl-3-chloro-1-methyl-but-3-enyl) -8-fluoro-quinoline-3-carboxamide +AX, Methyl (Z) -3-methoxy-2- [ 2-methyl-5- [4- (trifluoromethyl) triazol-2-yl ] phenoxy ] prop-2-enoate +AX, (Z) -3-methoxy-2- [ 2-methyl-5- (4-propyltriazol-2-yl) phenoxy ] prop-2-enoate +AX, (Z) -2- [5- (3-isopropylpyrazol-1-yl) -2-methyl-phenoxy ] -3-methoxy-prop-2-enoate +AX, (Z) -3-methoxy-2- [ 2-methyl-5- (3-propylpyrazol-1-yl) phenoxy ] prop-2-enoate +AX, Methyl (Z) -3-methoxy-2- [ 2-methyl-5- [3- (trifluoromethyl) pyrazol-1-yl ] phenoxy ] prop-2-enoate+ax, (Z) -2- (5-cyclohexyl-2-methyl-phenoxy) -3-methoxy-prop-2-enoate+ax, (Z) -2- (5-cyclopentyl-2-methyl-phenoxy) -3-methoxy-prop-2-enoate+ax, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -5-methyl-N-spiro [3.4] oct-3-yl-thiazole-4-carboxamide+ax, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide+ax, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -N-hexyl-5-methyl-thiazole-4-carboxamide +ax, 2- [ (2, 6-difluoro-4-pyridinyl) - (2-methoxyacetyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide +ax, 2- [ (2, 6-difluoro-4-pyridinyl) - (tetrahydropyran-4-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide +ax, 2- [ (2, 6-difluoro-4-pyridinyl) - (oxetane-3-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide +ax, 2- [ (2, 6-difluoro-4-pyridinyl) - (tetrahydrofuran-3-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide +AX, 2- [ acetyl- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide +AX, 2- [ (2, 6-difluoro-4-pyridinyl) - (2-methylpropanoyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide +AX, TAEGRO (i.e., bacillus amyloliquefaciens strain FZB 24) +AX, Melaleuca alternifolia oil (melaleuca alternifolia extract (commercially available as Timorex Gold; which is a broad-spectrum plant biological fungicide)) +ax, polygonum cuspidatum extract (commercially available as REGALIA) +ax, a plant extract based on a lycopodium clavatum extract (commercially available as BOTRISTOP) +ax and aureobasidin a+ax, wherein the ratio of component (a) to component (B) is from 100:1 to 1:40, preferably from 40:1 to 1:40, even more preferably from 20:1 to 1:20, Even more preferably from 15:1 to 1:30, even more preferably from 10:1 to 1:10, most preferably from 5:1 to 1:5 and even most preferably from 2:1 to 1:2.

In another embodiment of the invention, a mixture of component (a), wherein component (a) is a compound having formula (I), and component (B) is preferred as an active ingredient (wherein the term "AX" means a component (a) selected from the group consisting of a compound having formula (I), (I-a) or a compound selected from the group consisting of (x.01), (x.02), (x.03), (x.04), (x.05), (x.06), (x.07), (x.08), (x.09), (x.10), or (x.11), listed in table X according to the invention): TAEGRO (i.e. bacillus amyloliquefaciens strain FZB 24) +ax, melaleuca alternifolia oil (melaleuca alternifolia extract (commercially available as Timorex Gold) +ax, which is a broad spectrum plant biological fungicide)) +ax, a giant knotweed extract (commercially available as REGALIA) +ax, a plant extract based on lycopodophyllum as BOTRISTOP) +a, or a commodity +commodity.

In another embodiment of the invention, a mixture of component (A) (wherein component (A) is a compound of formula (I)) and component (B) is preferred as active ingredient (wherein the term "AX" means a component (A) selected from the group consisting of a compound of formula (I), (I-A) or a compound selected from the group consisting of (X.01), (X.02), (X.03), (X.04), (X.05), (X.06), (X.07), (X.08), (X.09), (X.10), or (X.11), listed in Table X according to the invention) TAEGRO (i.e., bacillus amyloliquefaciens strain FZB 24) +AX, melaleuca alternifolia oil (melaleuca alternifolia extract (as Timorex Gold) commercially available AX, which is a broad spectrum plant biological fungicide)) +AX, a giant knotweed extract (as REGALIA) +AX, a plant extract based on a stone tree extract (BOTRISTOP) as BOTRISTOP, or a commodity of a combination of elements (1+40) is preferred over the weight of component (A) to component (1).

In another preferred embodiment of the invention, a mixture of component (A), wherein component (A) is a compound of formula (I), and component (B), is preferred as active ingredient (wherein the term "AX" means a component (A) selected from the group consisting of a compound of formula (I), (I-A) or a compound selected from the group consisting of (X.01), (X.02), (X.03), (X.04), (X.05), (X.06), (X.07), (X.08), (X.09), (X.10), or (X.11), listed in Table X according to the invention) TAEGRO (i.e., bacillus amyloliquefaciens strain FZB 24) +AX, melaleuca alternifolia oil (tea plant melaleuca extract (commercially available as Timorex Gold.) +AX, which is a broad-spectrum plant biological fungicide), a giant knotweed extract (commercially available as REGALIA) +AX, a plant extract based on a rosewood extract (BOTRISTOP as BOTRISTOP AX), or a commodity of 1+40:.

In another more preferred embodiment of the present invention, a mixture of component (A), wherein component (A) is a compound having formula (I), and component (B) is preferred as an active ingredient (wherein the term "AX" means a component (A) selected from the group consisting of a compound having formula (I), (I-A) or a compound selected from the group consisting of (X.01), (X.02), (X.03), (X.04), (X.05), (X.06), (X.07), (X.08), (X.09), (X.10), or (X.11), listed in Table X according to the present invention): TAEGRO (i.e., bacillus amyloliquefaciens strain FZB 24) +AX, melaleuca alternifolia extract (commercially available as Timorex Gold)) +AX, a polygonum cuspidatum extract (commercially available as REGALIA) +AX, a plant extract based on alkali wood extract (BOTRISTOP as BOTRISTOP AX), or a commodity of 20+1 to 20 in weight percent of components (A).

In another even more preferred embodiment of the present invention, the following mixture of component (a) (wherein component (a) is a compound having formula (I)) and component (B) is preferred as active ingredient (wherein the term "AX" means one component (a) selected from the group consisting of: the compound having formula (I), (I-a) or a compound selected from (x.01), (x.02), (x.03), (x.04), (x.05), (x.06), (x.07), (x.08), (x.09), (x.10), or (x.11) listed in table X according to the invention): TAEGRO + (i.e., bacillus amyloliquefaciens strain FZB 24) +ax, melaleuca alternifolia oil (melaleuca alternifolia extract of tea plants (commercially available as Timorex Gold, which is a broad-spectrum plant biofungicide)), polygonum cuspidatum extract (commercially available as REGALIA) +ax, a plant extract based on a lycopodium extract (commercially available as BOTRISTOP) +ax, or aurin a+ax, wherein the weight ratio of component (a) to component (B) is from 20:1 to 1:20.

In another still more preferred embodiment of the invention, component (A) is compound number X.01, [5- (2, 4-difluorophenyl) -1,3, 4-thiadiazol-2-yl ] - [ (4R, 7S) -4, 7-dimethyl-4- (1-methylpyrazol-4-yl) -5, 7-dihydrothieno [2,3-c ] pyridin-6-yl ] methanone (X.01), or a salt enantiomer, tautomer, or N-oxide thereof, enantiomer, or N-oxide thereof, and component (B) is a compound selected from TAEGRO (i.e., bacillus amyloliquefaciens strain FZB 24), melaleuca alternifolia (tea plant melaleuca extract (commercially available as Timorex Gold), polygonum cuspidatum extract (commercially available as REGALIA), a plant extract based on lycobase extract (BOTRISTOP) as BOTRISTOP), or a basil extract (20) and wherein component (A) is preferably from group (40) by weight of component (A) is preferably from group (1) to (40).

In another still more preferred embodiment of the present invention, component (A) is compound number X.02, [5- (2, 4-difluorophenyl) isoxazol-3-yl ] - [ rac- (4S, 7R) -4, 7-dimethyl-4- (1-methylpyrazol-4-yl) -5, 7-dihydrothieno [2,3-c ] pyridin-6-yl ] methanone (X.02), or a salt enantiomer, tautomer, or N-oxide thereof, or enantiomer thereof, or N-oxide, and component (B) is a compound selected from TAEGRO (i.e., bacillus amyloliquefaciens strain FZB 24), melaleuca alternifolia oil (melaleuca alternifolia extract (commercially available as Timorex Gold), which is a broad spectrum plant biological fungicide), giant knotweed extract (commercially available as REGALIA), a plant extract based on a lycopodium extract (as BOTRISTOP), or a preferred ratio of component (A) to component (40) is from 1 to 20:40 by weight, preferably from component (A) to 20:40.

In another still more preferred embodiment of the invention, component (A) is compound number X.03 [5- (2, 4-difluorophenyl) isoxazol-3-yl ] - [ rac- (4R, 7S) -7-methyl-4- (1-methylpyrazol-4-yl) -5, 7-dihydro-4H-thieno [2,3-c ] pyridin-6-yl ] methanone (X.03), or a salt enantiomer, tautomer, or N-oxide thereof, enantiomer, or N-oxide thereof, and component (B) is a compound selected from the group consisting of TAEGRO (i.e., bacillus amyloliquefaciens strain FZB 24), melaleuca alternifolia extract (commercially available as Timorex Gold), giant knotweed extract (commercially available as REGALIA), a plant extract based on a lycopodium extract (BOTRISTOP), and a preferred ratio of components A to B (40) is from 1 to 40, preferably from 1 to 20.

In another still more preferred embodiment of the invention, component (A) is compound number X.04, [5- (2, 4-difluorophenyl) -1,3, 4-thiadiazol-2-yl ] - [ rac- (4R, 7S) -7-methyl-4- (1-methylpyrazol-4-yl) -5, 7-dihydro-4H-thieno [2,3-c ] pyridin-6-yl ] methanone (X.04), or a salt enantiomer, tautomer, or N-oxide thereof, and component (B) is a compound selected from the group consisting of TAEGRO (i.e., bacillus amyloliquefaciens strain FZB 24), melaleuca alternifolia (melaleuca alternifolia extract (commercially available as Timorex Gold), which is a broad spectrum plant biological fungicide), giant knotweed extract (commercially available as REGALIA), a plant extract based on a lycobase extract (as BOTRISTOP), and a basil extract (20:40), wherein the ratio by weight of component (A) to component (40:1) is preferably from 1:20:20.

In another still more preferred embodiment of the invention, component (A) is compound number X.05, [5- (2, 4-difluorophenyl) -1,3, 4-thiadiazol-2-yl ] - [ 4-methyl-4- (1-methylpyrazol-4-yl) -5, 7-dihydrothieno [2,3-c ] pyridin-6-yl ] methanone (X.05), or a salt enantiomer, tautomer, or N-oxide thereof, and component (B) is a compound selected from the group consisting of TAEGRO (i.e., bacillus amyloliquefaciens strain FZB 24), melaleuca alternifolia oil (Melaleuca alternifolia extract (commercially available as Timorex Gold, which is a broad-spectrum plant biological fungicide)), giant knotweed extract (commercially available as REGALIA), a plant extract based on a lycobase wood extract (commercially available as BOTRISTOP), or aurin A, wherein the weight ratio of component (A) to component (B) is from 1:40 to 20:1, preferably from 1:20.

In another still more preferred embodiment of the invention, component (A) is compound number X.06 [5- (2, 4-difluorophenyl) isoxazol-3-yl ] - [ 4-methyl-4- (1-methylpyrazol-4-yl) -5, 7-dihydrothieno [2,3-c ] pyridin-6-yl ] methanone (X.06), or a salt enantiomer, tautomer, or N-oxide thereof, and component (B) is a compound selected from the group consisting of TAEGRO (i.e., bacillus amyloliquefaciens strain FZB 24), melaleuca alternifolia oil (melaleuca alternifolia extract (commercially available as Timorex Gold, which is a broad-spectrum plant biological fungicide)), giant knotweed extract (commercially available as REGALIA), a plant extract based on a lycopodium extract (commercially available as BOTRISTOP), or a aurin A, wherein the weight ratio of component (A) to component (B) is from 1 to 40:1, preferably from 1 to 20:20.

In another still more preferred embodiment of the invention, component (A) is compound number X.07, [5- (2, 4-difluorophenyl) isoxazol-3-yl ] - [ 7-methyl-7- (1-methylpyrazol-4-yl) -4, 6-dihydrothieno [3,2-c ] pyridin-5-yl ] methanone (X.07), or a salt enantiomer, tautomer, or N-oxide thereof, and component (B) is a compound selected from TAEGRO (i.e., bacillus amyloliquefaciens strain FZB 24), melaleuca alternifolia oil (melaleuca alternifolia extract (commercially available as Timorex Gold, which is a broad-spectrum plant biological fungicide)), giant knotweed extract (commercially available as REGALIA), a plant extract based on a lycopodium extract (commercially available as BOTRISTOP), or a aurin A, wherein the weight ratio of component (A) to component (B) is from 1:40 to 40, preferably from 1:20:20.

In another still more preferred embodiment of the invention, component (A) is compound number X.08, [5- (2, 4-difluorophenyl) isoxazol-3-yl ] - [4- (1-methylpyrazol-4-yl) -5, 7-dihydro-4H-isothiazolo [5,4-c ] pyridin-6-yl ] methanone (X.08), or a salt enantiomer, tautomer, or N-oxide thereof, and component (B) is a compound selected from the group consisting of TAEGRO (i.e., bacillus amyloliquefaciens strain FZB 24), melaleuca alternifolia oil (melaleuca alternifolia extract (commercially available as Timorex Gold, which is a broad-spectrum plant biological fungicide), polygonum cuspidatum extract (commercially available as REGALIA), a plant extract based on a lycopodium extract (commercially available as BOTRISTOP), or a basil A, wherein the weight ratio of component (A) to component (B) is from 1 to 40:1, preferably from 1 to 20:20.

In another still more preferred embodiment of the invention, component (A) is compound number X.09, [5- (2, 4-difluorophenyl) isoxazol-3-yl ] - [7- (1, 5-dimethylpyrazol-4-yl) -6, 7-dihydro-4H-thiadiazolo [4,5-c ] pyridin-5-yl ] methanone (X.09), or a salt enantiomer, tautomer, or N-oxide thereof, and component (B) is a compound selected from the group consisting of TAEGRO (i.e., bacillus amyloliquefaciens strain FZB 24), melaleuca alternifolia oil (Melaleuca alternifolia extract (commercially available as Timorex Gold, which is a broad-spectrum plant biological fungicide)), giant knotweed extract (commercially available as REGALIA), a plant extract based on a lycobase wood extract (commercially available as BOTRISTOP), or gold basil A, wherein the weight ratio of component (A) to component (B) is from 1:40 to 20:1, preferably from 1:20.

In another still more preferred embodiment of the invention, component (A) is compound number X.10, [5- (2, 4-difluorophenyl) isoxazol-3-yl ] - [7- (1, 5-dimethylpyrazol-4-yl) -6, 7-dihydro-4H-thieno [3,2-c ] pyridin-5-yl ] methanone (X.10), or a salt enantiomer, tautomer, or N-oxide thereof, and component (B) is a compound selected from TAEGRO (i.e., bacillus amyloliquefaciens strain FZB 24), melaleuca alternifolia (tea plant melaleuca extract (commercially available as Timorex Gold), which is a broad-spectrum plant biological fungicide), giant knotweed extract (commercially available as REGALIA), a plant extract based on a lycopodium extract (commercially available as BOTRISTOP), or a gold basil A, wherein the weight ratio of component (A) to component (B) is from 1 to 20:40, preferably from 1:20:40.

In another still more preferred embodiment of the present invention, component (A) is compound number X.11, [5- (2, 4-difluorophenyl) isoxazol-3-yl ] - [ rac- (4S, 7S) -7- (1, 5-dimethylpyrazol-4-yl) -4-methyl-6, 7-dihydro-4H-thieno [3,2-c ] pyridin-5-yl ] methanone, or a salt enantiomer, tautomer, or N-oxide thereof, and component (B) is a compound selected from the group consisting of TAEGRO (i.e., bacillus amyloliquefaciens strain FZB 24), melaleuca alternifolia oil (melaleuca alternifolia extract (commercially available as Timorex Gold, which is a broad spectrum plant biological fungicide)), giant knotweed extract (commercially available as REGALIA), a plant extract based on a lycobase extract (commercially available as BOTRISTOP), or a gold basil A, wherein the weight ratio of component (A) to component (B) is from 1 to 20, preferably from 1 to 20, and from 1 to 20.

In a preferred composition according to the invention component (A) is compound number X.01, [5- (2, 4-difluorophenyl) -1,3, 4-thiadiazol-2-yl ] - [ (4R, 7S) -4, 7-methyl-4- (1-methylpyrazol-4-yl) -5, 7-dihydrothieno [2,3-c ] pyridin-6-yl ] methanone (X.01), or a salt enantiomer, tautomer, or N-oxide thereof, and component (B) is a compound selected from the group consisting of fluxapyroxal hydroxylamine, benzovindiflupyr, bixafen, fluxapyroxad, isopyrazam, penthiopyrad, Cyproconazole, boscalid, fluopyram, thiaflufenamide, bixafen, flufenamid, and flufenamid, and the like penflufen, indene penflufen, fluoxastrobin, trifluoracetam, and iprovalicarb, indene pencycuron penflufen, triflumizole, penflufen and the like cyproconazole, difenoconazole, metconazole, penconazole, propiconazole, tebuconazole, difenoconazole, prothioconazole, penconazole, trifloxystrobin, triflumizole, iprovalicarb, quinoline trifloxystrobin, metalaxyl-M, cyprodinil, pyrimethanil, mancozeb, copper compounds (different salts), sulfur, folpet, chlorothalonil, dithianon, Propoxyquinoline, fludioxonil, benzofuranone, fluorothiazolyl pyrithione, trifloxysulfate, alamic acid type benzene-S-methyl, phosphorous acid, cyflufenamid, tricyclazole, N-methoxy-N- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] cyclopropanecarboxamide, N, 2-dimethoxy-N- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] propionamide, 1-methoxy-3-methyl-1- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] urea, 1, 3-dimethoxy-1- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] urea, N- [ (1R) -1-benzyl-3-chloro-1-methyl-but-3-enyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-3-chloro-1-methyl-but-3-enyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1R) -1-benzyl-3, 3-trifluoro-1-methyl-propyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-3, 3-trifluoro-1-methyl-propyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl ] -7, 8-difluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-1, 3-dimethyl-butyl ] -7, 8-difluoro-quinoline-3-carboxamide, 8-fluoro-N- [ (1R) -1- [ (3-fluorophenyl) methyl ] -1, 3-dimethyl-butyl ] quinoline-3-carboxamide, 8-fluoro-N- [ (1S) -1- [ (3-fluorophenyl) methyl ] -1, 3-dimethyl-butyl ] quinoline-3-carboxamide, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, N- ((1R) -1-benzyl-3-chloro-1-methyl-but-3-enyl) -8-fluoro-quinoline-3-carboxamide, N- ((1S) -1-benzyl-3-chloro-1-methyl-but-3-enyl) -8-fluoro-quinoline-3-carboxamide, (Z) -3-methoxy-2- [ 2-methyl-5- [4- (trifluoromethyl) triazol-2-yl ] phenoxy ] prop-2-enoic acid methyl ester, (Z) -3-methoxy-2- [ 2-methyl-5- (4-propyltriazol-2-yl) phenoxy ] prop-2-enoic acid methyl ester, (Z) -2- [5- (3-isopropylpyrazol-1-yl) -2-methyl-phenoxy ] -3-methoxy-prop-2-enoic acid methyl ester, Methyl (Z) -3-methoxy-2- [ 2-methyl-5- (3-propylpyrazol-1-yl) phenoxy ] prop-2-enoate, methyl (Z) -3-methoxy-2- [ 2-methyl-5- [3- (trifluoromethyl) pyrazol-1-yl ] phenoxy ] prop-2-enoate, methyl (Z) -2- (5-cyclohexyl-2-methyl-phenoxy) -3-methoxy-prop-2-enoate, methyl (Z) -2- (5-cyclopentyl-2-methyl-phenoxy) -3-methoxy-prop-2-enoate (these compounds can be prepared by the methods described in WO 2020/193387), methyl (Z) -3-methoxy-prop-2-enoate, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -5-methyl-N-spiro [3.4] oct-3-yl-thiazole-4-carboxamide, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -N-hexyl-5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (2-methoxyacetyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (tetrahydropyran-4-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (oxetane-3-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (tetrahydrofuran-3-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ acetyl- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (2-methylpropanoyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, TAEGRO (i.e. bacillus amyloliquefaciens strain FZB 24), melaleuca alternifolia oil (melaleuca alternifolia extract (commercially available as Timorex Gold, which is a broad-spectrum plant biological fungicide)), giant knotweed extract (commercially available as REGALIA), a plant extract based on a lycopodium clavatum extract (commercially available as BOTRISTOP), or aureobasidin a, wherein the weight ratio of component (a) to component (B) is from 15:1 to 1:30.

In another preferred composition according to the invention, component (A) is compound number X.02- [5- (2, 4-difluorophenyl) isoxazol-3-yl ] - [ rac- (4S, 7R) -4, 7-dimethyl-4- (1-methylpyrazol-4-yl) -5, 7-dihydrothieno [2,3-c ] pyridin-6-yl ] methanone (X.02), or a salt enantiomer, tautomer, or N-oxide thereof, and component (B) is a compound selected from the group consisting of fluxapyroxad hydroxylamine, benzovindiflupyr, bixafen, fluxapyroxad, isopyrazamide, penthiopyrad, Cyproconazole, boscalid, fluopyram, thiaflufenamide, bixafen, flufenamid, and flufenamid, and the like penflufen, indene penflufen, fluoxastrobin, trifluoracetam, and iprovalicarb, indene pencycuron penflufen, triflumizole, penflufen and the like cyproconazole, difenoconazole, metconazole, penconazole, propiconazole, tebuconazole, difenoconazole, prothioconazole, penconazole, trifloxystrobin, triflumizole, iprovalicarb, quinoline trifloxystrobin, metalaxyl-M, cyprodinil, pyrimethanil, mancozeb, copper compounds (different salts), sulfur, folpet, chlorothalonil, dithianon, Propoxyquinoline, fludioxonil, benzofuranone, fluorothiazolyl pyrithione, trifloxysulfate, alamic acid type benzene-S-methyl, phosphorous acid, cyflufenamid, tricyclazole, N-methoxy-N- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] cyclopropanecarboxamide, N, 2-dimethoxy-N- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] propionamide, 1-methoxy-3-methyl-1- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] urea, 1, 3-dimethoxy-1- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] urea, N- [ (1R) -1-benzyl-3-chloro-1-methyl-but-3-enyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-3-chloro-1-methyl-but-3-enyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1R) -1-benzyl-3, 3-trifluoro-1-methyl-propyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-3, 3-trifluoro-1-methyl-propyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl ] -7, 8-difluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-1, 3-dimethyl-butyl ] -7, 8-difluoro-quinoline-3-carboxamide, 8-fluoro-N- [ (1R) -1- [ (3-fluorophenyl) methyl ] -1, 3-dimethyl-butyl ] quinoline-3-carboxamide, 8-fluoro-N- [ (1S) -1- [ (3-fluorophenyl) methyl ] -1, 3-dimethyl-butyl ] quinoline-3-carboxamide, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, N- ((1R) -1-benzyl-3-chloro-1-methyl-but-3-enyl) -8-fluoro-quinoline-3-carboxamide, N- ((1S) -1-benzyl-3-chloro-1-methyl-but-3-enyl) -8-fluoro-quinoline-3-carboxamide, (Z) -3-methoxy-2- [ 2-methyl-5- [4- (trifluoromethyl) triazol-2-yl ] phenoxy ] prop-2-enoic acid methyl ester, (Z) -3-methoxy-2- [ 2-methyl-5- (4-propyltriazol-2-yl) phenoxy ] prop-2-enoic acid methyl ester, (Z) -2- [5- (3-isopropylpyrazol-1-yl) -2-methyl-phenoxy ] -3-methoxy-prop-2-enoic acid methyl ester, Methyl (Z) -3-methoxy-2- [ 2-methyl-5- (3-propylpyrazol-1-yl) phenoxy ] prop-2-enoate, methyl (Z) -3-methoxy-2- [ 2-methyl-5- [3- (trifluoromethyl) pyrazol-1-yl ] phenoxy ] prop-2-enoate, methyl (Z) -2- (5-cyclohexyl-2-methyl-phenoxy) -3-methoxy-prop-2-enoate, methyl (Z) -2- (5-cyclopentyl-2-methyl-phenoxy) -3-methoxy-prop-2-enoate (these compounds can be prepared by the methods described in WO 2020/193387), methyl (Z) -3-methoxy-prop-2-enoate, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -5-methyl-N-spiro [3.4] oct-3-yl-thiazole-4-carboxamide, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -N-hexyl-5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (2-methoxyacetyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (tetrahydropyran-4-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (oxetane-3-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (tetrahydrofuran-3-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ acetyl- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (2-methylpropanoyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, TAEGRO (i.e. bacillus amyloliquefaciens strain FZB 24), melaleuca alternifolia oil (melaleuca alternifolia extract (commercially available as Timorex Gold, which is a broad-spectrum plant biological fungicide)), giant knotweed extract (commercially available as REGALIA), a plant extract based on a lycopodium clavatum extract (commercially available as BOTRISTOP), or aureobasidin a, wherein the weight ratio of component (a) to component (B) is from 15:1 to 1:30.

In another preferred composition according to the invention component (A) is compound number X.03 [5- (2, 4-difluorophenyl) isoxazol-3-yl ] - [ rac- (4R, 7S) -7-methyl-4- (1-methylpyrazol-4-yl) -5, 7-dihydro-4H-thieno [2,3-c ] pyridin-6-yl ] methanone (X.03), or a salt enantiomer, tautomer, or N-oxide thereof, and component (B) is a compound selected from the group consisting of fluxapyroxal hydroxylamine, benzovindiflupyr, bixafen, fluxapyroxad, isopyrazamide, penthiopyrad, Cyproconazole, boscalid, fluopyram, thiaflufenamide, bixafen, flufenamid, and flufenamid, and the like penflufen, indene penflufen, fluoxastrobin, trifluoracetam, and iprovalicarb, indene pencycuron penflufen, triflumizole, penflufen and the like cyproconazole, difenoconazole, metconazole, penconazole, propiconazole, tebuconazole, difenoconazole, prothioconazole, penconazole, trifloxystrobin, triflumizole, iprovalicarb, quinoline trifloxystrobin, metalaxyl-M, cyprodinil, pyrimethanil, mancozeb, copper compounds (different salts), sulfur, folpet, chlorothalonil, dithianon, Propoxyquinoline, fludioxonil, benzofuranone, fluorothiazolyl pyrithione, trifloxysulfate, alamic acid type benzene-S-methyl, phosphorous acid, cyflufenamid, tricyclazole, N-methoxy-N- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] cyclopropanecarboxamide, N, 2-dimethoxy-N- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] propionamide, 1-methoxy-3-methyl-1- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] urea, 1, 3-dimethoxy-1- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] urea, N- [ (1R) -1-benzyl-3-chloro-1-methyl-but-3-enyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-3-chloro-1-methyl-but-3-enyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1R) -1-benzyl-3, 3-trifluoro-1-methyl-propyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-3, 3-trifluoro-1-methyl-propyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl ] -7, 8-difluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-1, 3-dimethyl-butyl ] -7, 8-difluoro-quinoline-3-carboxamide, 8-fluoro-N- [ (1R) -1- [ (3-fluorophenyl) methyl ] -1, 3-dimethyl-butyl ] quinoline-3-carboxamide, 8-fluoro-N- [ (1S) -1- [ (3-fluorophenyl) methyl ] -1, 3-dimethyl-butyl ] quinoline-3-carboxamide, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, N- ((1R) -1-benzyl-3-chloro-1-methyl-but-3-enyl) -8-fluoro-quinoline-3-carboxamide, N- ((1S) -1-benzyl-3-chloro-1-methyl-but-3-enyl) -8-fluoro-quinoline-3-carboxamide, (Z) -3-methoxy-2- [ 2-methyl-5- [4- (trifluoromethyl) triazol-2-yl ] phenoxy ] prop-2-enoic acid methyl ester, (Z) -3-methoxy-2- [ 2-methyl-5- (4-propyltriazol-2-yl) phenoxy ] prop-2-enoic acid methyl ester, (Z) -2- [5- (3-isopropylpyrazol-1-yl) -2-methyl-phenoxy ] -3-methoxy-prop-2-enoic acid methyl ester, Methyl (Z) -3-methoxy-2- [ 2-methyl-5- (3-propylpyrazol-1-yl) phenoxy ] prop-2-enoate, methyl (Z) -3-methoxy-2- [ 2-methyl-5- [3- (trifluoromethyl) pyrazol-1-yl ] phenoxy ] prop-2-enoate, methyl (Z) -2- (5-cyclohexyl-2-methyl-phenoxy) -3-methoxy-prop-2-enoate, methyl (Z) -2- (5-cyclopentyl-2-methyl-phenoxy) -3-methoxy-prop-2-enoate (these compounds can be prepared by the methods described in WO 2020/193387), methyl (Z) -3-methoxy-prop-2-enoate, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -5-methyl-N-spiro [3.4] oct-3-yl-thiazole-4-carboxamide, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -N-hexyl-5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (2-methoxyacetyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (tetrahydropyran-4-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (oxetane-3-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (tetrahydrofuran-3-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ acetyl- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (2-methylpropanoyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, TAEGRO (i.e. bacillus amyloliquefaciens strain FZB 24), melaleuca alternifolia oil (melaleuca alternifolia extract (commercially available as Timorex Gold, which is a broad-spectrum plant biological fungicide)), giant knotweed extract (commercially available as REGALIA), a plant extract based on a lycopodium clavatum extract (commercially available as BOTRISTOP), or aureobasidin a, wherein the weight ratio of component (a) to component (B) is from 15:1 to 1:30.

In another preferred composition according to the invention component (A) is compound number X.04, [5- (2, 4-difluorophenyl) -1,3, 4-thiadiazol-2-yl ] - [ rac- (4R, 7S) -7-methyl-4- (1-methylpyrazol-4-yl) -5, 7-dihydro-4H-thieno [2,3-c ] pyridin-6-yl ] methanone (X.04), or a salt enantiomer, tautomer, or N-oxide thereof, and component (B) is a compound selected from the group consisting of fluxapyroxad hydroxylamine, benzovindiflupyr, bixafen, fluxapyroxad, Isopyrazam, penthiopyrad, cyproconazole, boscalid, fluopyram, flupyraclostrobin, fluxapyroxad, fluxad, and the like thiaflufenamide, bixafen, ipflupyraclostrobin, indene picolinamine thiaflufenamide, bixafen, and other drugs iprovalicarb, indene pencycuron fenpropidin, cyproconazole, difenoconazole, metconazole, penconazole, cyproconazole, difenoconazole, metconazole, difenoconazole, metconazole propiconazole, tebuconazole, fluoroether azole, prothioconazole, penconazole, difenoconazole triflumizole, iprodione, triflumuron, metalaxyl-M, cyprodinil, pyrimethanil, mancozeb, copper compounds (different salts), sulfur, Folpet, chlorothalonil, dithianon, propoxyquinoline, fludioxonil, phenomenon, fluorothiazolyl ethanone, fluorooxamate sulphonyl, alamic acid type benzene-S-methyl, phosphorous acid, cyflufenamid, tricyclazole, N-methoxy-N- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] cyclopropanecarboxamide, N, 2-dimethoxy-N- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] propionamide, 1-methoxy-3-methyl-1- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] urea, 1, 3-dimethoxy-1- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] urea, N- [ (1R) -1-benzyl-3-chloro-1-methyl-but-3-enyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-3-chloro-1-methyl-but-3-enyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1R) -1-benzyl-3, 3-trifluoro-1-methyl-propyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-3, 3-trifluoro-1-methyl-propyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl ] -7, 8-difluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-1, 3-dimethyl-butyl ] -7, 8-difluoro-quinoline-3-carboxamide, 8-fluoro-N- [ (1R) -1- [ (3-fluorophenyl) methyl ] -1, 3-dimethyl-butyl ] quinoline-3-carboxamide, 8-fluoro-N- [ (1S) -1- [ (3-fluorophenyl) methyl ] -1, 3-dimethyl-butyl ] quinoline-3-carboxamide, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, N- ((1R) -1-benzyl-3-chloro-1-methyl-but-3-enyl) -8-fluoro-quinoline-3-carboxamide, N- ((1S) -1-benzyl-3-chloro-1-methyl-but-3-enyl) -8-fluoro-quinoline-3-carboxamide, (Z) -3-methoxy-2- [ 2-methyl-5- [4- (trifluoromethyl) triazol-2-yl ] phenoxy ] prop-2-enoic acid methyl ester, (Z) -3-methoxy-2- [ 2-methyl-5- (4-propyltriazol-2-yl) phenoxy ] prop-2-enoic acid methyl ester, (Z) -2- [5- (3-Isopropylpyrazol-1-yl) -2-methyl-phenoxy ] -3-methoxy-prop-2-enoic acid methyl ester, (Z) -3-methoxy-2- [ 2-methyl-5- (3-propylpyrazol-1-yl) phenoxy ] prop-2-enoic acid methyl ester, (Z) -3-methoxy-2- [ 2-methyl-5- [3- (trifluoromethyl) pyrazol-1-yl ] phenoxy ] prop-2-enoic acid methyl ester, (Z) -2- (5-cyclohexyl-2-methyl-phenoxy) -3-methoxy-prop-2-enoic acid methyl ester, (Z) -2- (5-cyclopentyl-2-methyl-phenoxy) -3-methoxy-prop-2-enoic acid methyl ester (these compounds can be prepared by the methods described in WO 2020/193387), 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -5-methyl-N-spiro [3.4] oct-3-yl-thiazole-4-carboxamide, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -N-hexyl-5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (2-methoxyacetyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (tetrahydropyran-4-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (oxetane-3-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (tetrahydrofuran-3-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ acetyl- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (2-methylpropanoyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, TAEGRO (i.e. bacillus amyloliquefaciens strain FZB 24), melaleuca alternifolia oil (melaleuca alternifolia extract (commercially available as Timorex Gold, which is a broad-spectrum plant biological fungicide)), giant knotweed extract (commercially available as REGALIA), a plant extract based on a lycopodium clavatum extract (commercially available as BOTRISTOP), or aureobasidin a, wherein the weight ratio of component (a) to component (B) is from 15:1 to 1:30.

In another preferred composition according to the invention component (A) is compound number X.05, [5- (2, 4-difluorophenyl) -1,3, 4-thiadiazol-2-yl ] - [ 4-methyl-4- (1-methylpyrazol-4-yl) -5, 7-dihydrothieno [2,3-c ] pyridin-6-yl ] methanone (X.05), or a salt enantiomer, tautomer, or N-oxide thereof, and component (B) is a compound selected from the group consisting of fluxapyroxad hydroxylamine, benzovindiflupyr, bipyramid, fluxapyroxad, isopyrazamide, penthiopyrad, epothilone, Trifloxystrobin, azoxystrobin, tetrazolidone picolide, picolinamide trifloxystrobin, azoxystrobin, tetrazolidone, picolide, picolinamide, trifloxystrobin, picolinamide, and pyrad hoc, or mixtures thereof Pyridinamide, fluazinam, fenpropidin, cyproconazole difenoconazole, metconazole, penconazole, propiconazole, tebuconazole, penconazole, prothioconazole, penoxsulam, triflumizole, triflumuron, iprovalicarb, triflumuron, metalaxyl-M, cyprodinil, pyrimethanil, mancozeb, copper compounds (different salts), sulfur, folpet, chlorothalonil, dithianon, propioquinoline, trifloxystrobin, Fludioxonil, benzofuranone, fluorothiazolyl ethanone, trifloxysulf, alamic acid type benzene-S-methyl, phosphorous acid, cyflufenamid, tricyclazole, N-methoxy-N- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] cyclopropanecarboxamide, N, 2-dimethoxy-N- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] propionamide, 1-methoxy-3-methyl-1- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] urea, 1, 3-dimethoxy-1- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] urea, N- [ (1R) -1-benzyl-3-chloro-1-methyl-but-3-enyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-3-chloro-1-methyl-but-3-enyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1R) -1-benzyl-3, 3-trifluoro-1-methyl-propyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-3, 3-trifluoro-1-methyl-propyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl ] -7, 8-difluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-1, 3-dimethyl-butyl ] -7, 8-difluoro-quinoline-3-carboxamide, 8-fluoro-N- [ (1R) -1- [ (3-fluorophenyl) methyl ] -1, 3-dimethyl-butyl ] quinoline-3-carboxamide, 8-fluoro-N- [ (1S) -1- [ (3-fluorophenyl) methyl ] -1, 3-dimethyl-butyl ] quinoline-3-carboxamide, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, N- ((1R) -1-benzyl-3-chloro-1-methyl-but-3-enyl) -8-fluoro-quinoline-3-carboxamide, N- ((1S) -1-benzyl-3-chloro-1-methyl-but-3-enyl) -8-fluoro-quinoline-3-carboxamide, (Z) -3-methoxy-2- [ 2-methyl-5- [4- (trifluoromethyl) triazol-2-yl ] phenoxy ] prop-2-enoic acid methyl ester, (Z) -3-methoxy-2- [ 2-methyl-5- (4-propyltriazol-2-yl) phenoxy ] prop-2-enoic acid methyl ester, (Z) -2- [5- (3-isopropylpyrazol-1-yl) -2-methyl-phenoxy ] -3-methoxy-prop-2-enoic acid methyl ester, Methyl (Z) -3-methoxy-2- [ 2-methyl-5- (3-propylpyrazol-1-yl) phenoxy ] prop-2-enoate, methyl (Z) -3-methoxy-2- [ 2-methyl-5- [3- (trifluoromethyl) pyrazol-1-yl ] phenoxy ] prop-2-enoate, methyl (Z) -2- (5-cyclohexyl-2-methyl-phenoxy) -3-methoxy-prop-2-enoate, methyl (Z) -2- (5-cyclopentyl-2-methyl-phenoxy) -3-methoxy-prop-2-enoate (these compounds can be prepared by the methods described in WO 2020/193387), methyl (Z) -3-methoxy-prop-2-enoate, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -5-methyl-N-spiro [3.4] oct-3-yl-thiazole-4-carboxamide, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -N-hexyl-5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (2-methoxyacetyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (tetrahydropyran-4-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (oxetane-3-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (tetrahydrofuran-3-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ acetyl- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (2-methylpropanoyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, TAEGRO (i.e. bacillus amyloliquefaciens strain FZB 24), melaleuca alternifolia oil (melaleuca alternifolia extract (commercially available as Timorex Gold, which is a broad-spectrum plant biological fungicide)), giant knotweed extract (commercially available as REGALIA), a plant extract based on a lycopodium clavatum extract (commercially available as BOTRISTOP), or aureobasidin a, wherein the weight ratio of component (a) to component (B) is from 15:1 to 1:30.

In another preferred composition according to the invention, component (A) is compound number X.06: [5- (2, 4-difluorophenyl) isoxazol-3-yl ] - [ 4-methyl-4- (1-methylpyrazol-4-yl) -5, 7-dihydrothieno [2,3-c ] pyridin-6-yl ] methanone (X.06), or a salt enantiomer, tautomer, or N-oxide thereof, and component (B) is a compound selected from the group consisting of fluxapyroxad hydroxylamine, benzovindiflupyr, bixafen, fluxapyroxad, isopyrazam, penthiopyrad, fluxapyroxad, cyproconazole, flupiroxicam, Picolide, picolinamide fluazinam, fenpropidin picolide, picolinamide, fluazinam, fenpropidin fenhexamid, cyproconazole, difenoconazole, metconazole, penconazole propiconazole, tebuconazole, epoxiconazole, prothioconazole, penflufen, triflumizole, iprovalicarb, triflumuron, metalaxyl-M, cyprodinil, pyrimethanil, mancozeb, copper compounds (different salts), sulfur, folpet, chlorothalonil, dithianon, propiquin, fludioxonil, metrafenone, fluzopyr-ethyl, Fungicide, alamic acid benzene-S-methyl, phosphorous acid, cyflufenamid, tricyclazole, N-methoxy-N- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] cyclopropanecarboxamide, N, 2-dimethoxy-N- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] propionamide, 1-methoxy-3-methyl-1- [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] urea, 1, 3-dimethoxy-1- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] urea, and process for preparing same, N- [ (1R) -1-benzyl-3-chloro-1-methyl-but-3-enyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-3-chloro-1-methyl-but-3-enyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1R) -1-benzyl-3, 3-trifluoro-1-methyl-propyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-3, 3-trifluoro-1-methyl-propyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl ] -7, 8-difluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-1, 3-dimethyl-butyl ] -7, 8-difluoro-quinoline-3-carboxamide, 8-fluoro-N- [ (1R) -1- [ (3-fluorophenyl) methyl ] -1, 3-dimethyl-butyl ] quinoline-3-carboxamide, 8-fluoro-N- [ (1S) -1- [ (3-fluorophenyl) methyl ] -1, 3-dimethyl-butyl ] quinoline-3-carboxamide, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, N- ((1R) -1-benzyl-3-chloro-1-methyl-but-3-enyl) -8-fluoro-quinoline-3-carboxamide, N- ((1S) -1-benzyl-3-chloro-1-methyl-but-3-enyl) -8-fluoro-quinoline-3-carboxamide, (Z) -3-methoxy-2- [ 2-methyl-5- [4- (trifluoromethyl) triazol-2-yl ] phenoxy ] prop-2-enoic acid methyl ester, (Z) -3-methoxy-2- [ 2-methyl-5- (4-propyltriazol-2-yl) phenoxy ] prop-2-enoic acid methyl ester, (Z) -2- [5- (3-isopropylpyrazol-1-yl) -2-methyl-phenoxy ] -3-methoxy-prop-2-enoic acid methyl ester, Methyl (Z) -3-methoxy-2- [ 2-methyl-5- (3-propylpyrazol-1-yl) phenoxy ] prop-2-enoate, methyl (Z) -3-methoxy-2- [ 2-methyl-5- [3- (trifluoromethyl) pyrazol-1-yl ] phenoxy ] prop-2-enoate, methyl (Z) -2- (5-cyclohexyl-2-methyl-phenoxy) -3-methoxy-prop-2-enoate, methyl (Z) -2- (5-cyclopentyl-2-methyl-phenoxy) -3-methoxy-prop-2-enoate (these compounds can be prepared by the methods described in WO 2020/193387), methyl (Z) -3-methoxy-prop-2-enoate, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -5-methyl-N-spiro [3.4] oct-3-yl-thiazole-4-carboxamide, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -N-hexyl-5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (2-methoxyacetyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (tetrahydropyran-4-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (oxetane-3-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (tetrahydrofuran-3-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ acetyl- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (2-methylpropanoyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, TAEGRO (i.e. bacillus amyloliquefaciens strain FZB 24), melaleuca alternifolia oil (melaleuca alternifolia extract (commercially available as Timorex Gold, which is a broad-spectrum plant biological fungicide)), giant knotweed extract (commercially available as REGALIA), a plant extract based on a lycopodium clavatum extract (commercially available as BOTRISTOP), or aureobasidin a, wherein the weight ratio of component (a) to component (B) is from 15:1 to 1:30.

In another preferred composition according to the invention, component (A) is compound number X.07, [5- (2, 4-difluorophenyl) isoxazol-3-yl ] - [ 7-methyl-7- (1-methylpyrazol-4-yl) -4, 6-dihydrothieno [3,2-c ] pyridin-5-yl ] methanone (X.07), or a salt enantiomer, tautomer, or N-oxide thereof, and component (B) is a compound selected from the group consisting of fluxapyroxad hydroxylamine, benzovindiflupyr, bixafen, fluxapyroxad, isopyrazam, penthiopyrad, epothilone, boscalid, fluopicolide, flupyraclostrobin, Picolide, picolinamide fluazinam, fenpropidin picolide, picolinamide, fluazinam, fenpropidin fenhexamid, cyproconazole, difenoconazole, metconazole, penconazole propiconazole, tebuconazole, epoxiconazole, prothioconazole, penflufen, triflumizole, iprovalicarb, triflumuron, metalaxyl-M, cyprodinil, pyrimethanil, mancozeb, copper compounds (different salts), sulfur, folpet, chlorothalonil, dithianon, propiquin, fludioxonil, metrafenone, fluzopyr-ethyl, Fungicide, alamic acid benzene-S-methyl, phosphorous acid, cyflufenamid, tricyclazole, N-methoxy-N- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] cyclopropanecarboxamide, N, 2-dimethoxy-N- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] propionamide, 1-methoxy-3-methyl-1- [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] urea, 1, 3-dimethoxy-1- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] urea, and process for preparing same, N- [ (1R) -1-benzyl-3-chloro-1-methyl-but-3-enyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-3-chloro-1-methyl-but-3-enyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1R) -1-benzyl-3, 3-trifluoro-1-methyl-propyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-3, 3-trifluoro-1-methyl-propyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl ] -7, 8-difluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-1, 3-dimethyl-butyl ] -7, 8-difluoro-quinoline-3-carboxamide, 8-fluoro-N- [ (1R) -1- [ (3-fluorophenyl) methyl ] -1, 3-dimethyl-butyl ] quinoline-3-carboxamide, 8-fluoro-N- [ (1S) -1- [ (3-fluorophenyl) methyl ] -1, 3-dimethyl-butyl ] quinoline-3-carboxamide, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, N- ((1R) -1-benzyl-3-chloro-1-methyl-but-3-enyl) -8-fluoro-quinoline-3-carboxamide, N- ((1S) -1-benzyl-3-chloro-1-methyl-but-3-enyl) -8-fluoro-quinoline-3-carboxamide, (Z) -3-methoxy-2- [ 2-methyl-5- [4- (trifluoromethyl) triazol-2-yl ] phenoxy ] prop-2-enoic acid methyl ester, (Z) -3-methoxy-2- [ 2-methyl-5- (4-propyltriazol-2-yl) phenoxy ] prop-2-enoic acid methyl ester, (Z) -2- [5- (3-isopropylpyrazol-1-yl) -2-methyl-phenoxy ] -3-methoxy-prop-2-enoic acid methyl ester, Methyl (Z) -3-methoxy-2- [ 2-methyl-5- (3-propylpyrazol-1-yl) phenoxy ] prop-2-enoate, methyl (Z) -3-methoxy-2- [ 2-methyl-5- [3- (trifluoromethyl) pyrazol-1-yl ] phenoxy ] prop-2-enoate, methyl (Z) -2- (5-cyclohexyl-2-methyl-phenoxy) -3-methoxy-prop-2-enoate, methyl (Z) -2- (5-cyclopentyl-2-methyl-phenoxy) -3-methoxy-prop-2-enoate (these compounds can be prepared by the methods described in WO 2020/193387), methyl (Z) -3-methoxy-prop-2-enoate, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -5-methyl-N-spiro [3.4] oct-3-yl-thiazole-4-carboxamide, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -N-hexyl-5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (2-methoxyacetyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (tetrahydropyran-4-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (oxetane-3-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (tetrahydrofuran-3-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ acetyl- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (2-methylpropanoyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, TAEGRO (i.e. bacillus amyloliquefaciens strain FZB 24), melaleuca alternifolia oil (melaleuca alternifolia extract (commercially available as Timorex Gold, which is a broad-spectrum plant biological fungicide)), giant knotweed extract (commercially available as REGALIA), a plant extract based on a lycopodium clavatum extract (commercially available as BOTRISTOP), or aureobasidin a, wherein the weight ratio of component (a) to component (B) is from 15:1 to 1:30.

In another preferred composition according to the invention component (A) is compound number X.08: [5- (2, 4-difluorophenyl) isoxazol-3-yl ] - [4- (1-methylpyrazol-4-yl) -5, 7-dihydro-4H-isothiazolo [5,4-c ] pyridin-6-yl ] methanone (X.08), or a salt enantiomer, tautomer, or N-oxide thereof, and component (B) is a compound selected from the group consisting of fluxazoxamide, benzovindiflupyr, bixafen, fluxapyroxad, isopyrazam, penthiopyrad, fluxapyroxad, boscalid, flupirfenmid, Picolide, picolinamide fluazinam, fenpropidin picolide, picolinamide, fluazinam, fenpropidin fenhexamid, cyproconazole, difenoconazole, metconazole, penconazole propiconazole, tebuconazole, epoxiconazole, prothioconazole, penflufen, triflumizole, iprovalicarb, triflumuron, metalaxyl-M, cyprodinil, pyrimethanil, mancozeb, copper compounds (different salts), sulfur, folpet, chlorothalonil, dithianon, propiquin, fludioxonil, metrafenone, fluzopyr-ethyl, Fungicide, alamic acid benzene-S-methyl, phosphorous acid, cyflufenamid, tricyclazole, N-methoxy-N- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] cyclopropanecarboxamide, N, 2-dimethoxy-N- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] propionamide, 1-methoxy-3-methyl-1- [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] urea, 1, 3-dimethoxy-1- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] urea, and process for preparing same, N- [ (1R) -1-benzyl-3-chloro-1-methyl-but-3-enyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-3-chloro-1-methyl-but-3-enyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1R) -1-benzyl-3, 3-trifluoro-1-methyl-propyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-3, 3-trifluoro-1-methyl-propyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl ] -7, 8-difluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-1, 3-dimethyl-butyl ] -7, 8-difluoro-quinoline-3-carboxamide, 8-fluoro-N- [ (1R) -1- [ (3-fluorophenyl) methyl ] -1, 3-dimethyl-butyl ] quinoline-3-carboxamide, 8-fluoro-N- [ (1S) -1- [ (3-fluorophenyl) methyl ] -1, 3-dimethyl-butyl ] quinoline-3-carboxamide, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, N- ((1R) -1-benzyl-3-chloro-1-methyl-but-3-enyl) -8-fluoro-quinoline-3-carboxamide, N- ((1S) -1-benzyl-3-chloro-1-methyl-but-3-enyl) -8-fluoro-quinoline-3-carboxamide, (Z) -3-methoxy-2- [ 2-methyl-5- [4- (trifluoromethyl) triazol-2-yl ] phenoxy ] prop-2-enoic acid methyl ester, (Z) -3-methoxy-2- [ 2-methyl-5- (4-propyltriazol-2-yl) phenoxy ] prop-2-enoic acid methyl ester, (Z) -2- [5- (3-isopropylpyrazol-1-yl) -2-methyl-phenoxy ] -3-methoxy-prop-2-enoic acid methyl ester, Methyl (Z) -3-methoxy-2- [ 2-methyl-5- (3-propylpyrazol-1-yl) phenoxy ] prop-2-enoate, methyl (Z) -3-methoxy-2- [ 2-methyl-5- [3- (trifluoromethyl) pyrazol-1-yl ] phenoxy ] prop-2-enoate, methyl (Z) -2- (5-cyclohexyl-2-methyl-phenoxy) -3-methoxy-prop-2-enoate, methyl (Z) -2- (5-cyclopentyl-2-methyl-phenoxy) -3-methoxy-prop-2-enoate (these compounds can be prepared by the methods described in WO 2020/193387), methyl (Z) -3-methoxy-prop-2-enoate, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -5-methyl-N-spiro [3.4] oct-3-yl-thiazole-4-carboxamide, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -N-hexyl-5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (2-methoxyacetyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (tetrahydropyran-4-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (oxetane-3-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (tetrahydrofuran-3-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ acetyl- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (2-methylpropanoyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, TAEGRO (i.e. bacillus amyloliquefaciens strain FZB 24), melaleuca alternifolia oil (melaleuca alternifolia extract (commercially available as Timorex Gold, which is a broad-spectrum plant biological fungicide)), giant knotweed extract (commercially available as REGALIA), a plant extract based on a lycopodium clavatum extract (commercially available as BOTRISTOP), or aureobasidin a, wherein the weight ratio of component (a) to component (B) is from 15:1 to 1:30.

In another preferred composition according to the invention component (A) is compound number X.09, [5- (2, 4-difluorophenyl) isoxazol-3-yl ] - [7- (1, 5-dimethylpyrazol-4-yl) -6, 7-dihydro-4H-thiadiazolo [4,5-c ] pyridin-5-yl ] methanone (X.09), or a salt enantiomer, tautomer, or N-oxide thereof, and component (B) is a compound selected from the group consisting of fluxapyroxad hydroxylamine, benzovindiflupyr, bipyramid, fluxapyroxad, isopyrazam, penthiopyrad, epoxiconamine, boscalid, fluxad, fluopicolide, thiaflufenamide, bixafen, iprovalicarb, indenopyrazolam, penconazole, triflumamid, pyraclostrobin, trifloxystrobin, azoxystrobin, tetrazolidone, picolide, picolinamide, fluazinam, fenpropidin, fenhexamid, cyproconazole, difenoconazole, trifloxystrobin, fenpropiconazole, fenpropion-methyl, and the like metconazole, penconazole, propiconazole, tebuconazole, penconazole, prothioconazole, penconazole, triflumizole, iprovalicarb, triflumuron, metalaxyl-M, cyprodinil, pyrimethanil, mancozeb, copper compounds (different salts), sulfur, folpet, chlorothalonil, dithianon, propioquinoline, fludioxonil, Benzofuranone, fluorothiazolyl ethanone, fluorooxazamate, alamic acid-benzene-S-methyl, phosphorous acid, cyflufenamid, tricyclazole, N-methoxy-N- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] cyclopropanecarboxamide, N, 2-dimethoxy-N- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] propionamide, 1-methoxy-3-methyl-1- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] urea, 1, 3-dimethoxy-1- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] urea, N- [ (1R) -1-benzyl-3-chloro-1-methyl-but-3-enyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-3-chloro-1-methyl-but-3-enyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1R) -1-benzyl-3, 3-trifluoro-1-methyl-propyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-3, 3-trifluoro-1-methyl-propyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl ] -7, 8-difluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-1, 3-dimethyl-butyl ] -7, 8-difluoro-quinoline-3-carboxamide, 8-fluoro-N- [ (1R) -1- [ (3-fluorophenyl) methyl ] -1, 3-dimethyl-butyl ] quinoline-3-carboxamide, 8-fluoro-N- [ (1S) -1- [ (3-fluorophenyl) methyl ] -1, 3-dimethyl-butyl ] quinoline-3-carboxamide, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, N- ((1R) -1-benzyl-3-chloro-1-methyl-but-3-enyl) -8-fluoro-quinoline-3-carboxamide, N- ((1S) -1-benzyl-3-chloro-1-methyl-but-3-enyl) -8-fluoro-quinoline-3-carboxamide, (Z) -3-methoxy-2- [ 2-methyl-5- [4- (trifluoromethyl) triazol-2-yl ] phenoxy ] prop-2-enoic acid methyl ester, (Z) -3-methoxy-2- [ 2-methyl-5- (4-propyltriazol-2-yl) phenoxy ] prop-2-enoic acid methyl ester, (Z) -2- [5- (3-isopropylpyrazol-1-yl) -2-methyl-phenoxy ] -3-methoxy-prop-2-enoic acid methyl ester, Methyl (Z) -3-methoxy-2- [ 2-methyl-5- (3-propylpyrazol-1-yl) phenoxy ] prop-2-enoate, methyl (Z) -3-methoxy-2- [ 2-methyl-5- [3- (trifluoromethyl) pyrazol-1-yl ] phenoxy ] prop-2-enoate, methyl (Z) -2- (5-cyclohexyl-2-methyl-phenoxy) -3-methoxy-prop-2-enoate, methyl (Z) -2- (5-cyclopentyl-2-methyl-phenoxy) -3-methoxy-prop-2-enoate (these compounds can be prepared by the methods described in WO 2020/193387), methyl (Z) -3-methoxy-prop-2-enoate, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -5-methyl-N-spiro [3.4] oct-3-yl-thiazole-4-carboxamide, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -N-hexyl-5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (2-methoxyacetyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (tetrahydropyran-4-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (oxetane-3-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (tetrahydrofuran-3-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ acetyl- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (2-methylpropanoyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, TAEGRO (i.e. bacillus amyloliquefaciens strain FZB 24), melaleuca alternifolia oil (melaleuca alternifolia extract (commercially available as Timorex Gold, which is a broad-spectrum plant biological fungicide)), giant knotweed extract (commercially available as REGALIA), a plant extract based on a lycopodium clavatum extract (commercially available as BOTRISTOP), or aureobasidin a, wherein the weight ratio of component (a) to component (B) is from 15:1 to 1:30.

In another preferred composition according to the invention component (A) is compound number X.10, [5- (2, 4-difluorophenyl) isoxazol-3-yl ] - [7- (1, 5-dimethylpyrazol-4-yl) -6, 7-dihydro-4H-thieno [3,2-c ] pyridin-5-yl ] methanone (X.10), or a salt enantiomer, tautomer, or N-oxide thereof, and component (B) is a compound selected from the group consisting of fluxapyroxad hydroxylamine, benzovindiflupyr, bixafen, fluxapyroxad, isopyrazam, penthiopyrad, fluxapyroxad, boscalid, fluxad, fluxapyroxad, fluopicolide, thiaflufenamide, bixafen, iprovalicarb, indenopyrazolam, penconazole, triflumamid, pyraclostrobin, trifloxystrobin, azoxystrobin, tetrazolidone, picolide, picolinamide, fluazinam, fenpropidin, fenhexamid, cyproconazole, difenoconazole, trifloxystrobin, fenpropiconazole, fenpropion-methyl, and the like metconazole, penconazole, propiconazole, tebuconazole, penconazole, prothioconazole, penconazole, triflumizole, iprovalicarb, triflumuron, metalaxyl-M, cyprodinil, pyrimethanil, mancozeb, copper compounds (different salts), sulfur, folpet, chlorothalonil, dithianon, propioquinoline, fludioxonil, Benzofuranone, fluorothiazolyl ethanone, fluorooxazamate, alamic acid-benzene-S-methyl, phosphorous acid, cyflufenamid, tricyclazole, N-methoxy-N- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] cyclopropanecarboxamide, N, 2-dimethoxy-N- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] propionamide, 1-methoxy-3-methyl-1- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] urea, 1, 3-dimethoxy-1- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] urea, N- [ (1R) -1-benzyl-3-chloro-1-methyl-but-3-enyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-3-chloro-1-methyl-but-3-enyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1R) -1-benzyl-3, 3-trifluoro-1-methyl-propyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-3, 3-trifluoro-1-methyl-propyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl ] -7, 8-difluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-1, 3-dimethyl-butyl ] -7, 8-difluoro-quinoline-3-carboxamide, 8-fluoro-N- [ (1R) -1- [ (3-fluorophenyl) methyl ] -1, 3-dimethyl-butyl ] quinoline-3-carboxamide, 8-fluoro-N- [ (1S) -1- [ (3-fluorophenyl) methyl ] -1, 3-dimethyl-butyl ] quinoline-3-carboxamide, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, N- ((1R) -1-benzyl-3-chloro-1-methyl-but-3-enyl) -8-fluoro-quinoline-3-carboxamide, N- ((1S) -1-benzyl-3-chloro-1-methyl-but-3-enyl) -8-fluoro-quinoline-3-carboxamide, (Z) -3-methoxy-2- [ 2-methyl-5- [4- (trifluoromethyl) triazol-2-yl ] phenoxy ] prop-2-enoic acid methyl ester, (Z) -3-methoxy-2- [ 2-methyl-5- (4-propyltriazol-2-yl) phenoxy ] prop-2-enoic acid methyl ester, (Z) -2- [5- (3-isopropylpyrazol-1-yl) -2-methyl-phenoxy ] -3-methoxy-prop-2-enoic acid methyl ester, Methyl (Z) -3-methoxy-2- [ 2-methyl-5- (3-propylpyrazol-1-yl) phenoxy ] prop-2-enoate, methyl (Z) -3-methoxy-2- [ 2-methyl-5- [3- (trifluoromethyl) pyrazol-1-yl ] phenoxy ] prop-2-enoate, methyl (Z) -2- (5-cyclohexyl-2-methyl-phenoxy) -3-methoxy-prop-2-enoate, methyl (Z) -2- (5-cyclopentyl-2-methyl-phenoxy) -3-methoxy-prop-2-enoate (these compounds can be prepared by the methods described in WO 2020/193387), methyl (Z) -3-methoxy-prop-2-enoate, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -5-methyl-N-spiro [3.4] oct-3-yl-thiazole-4-carboxamide, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -N-hexyl-5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (2-methoxyacetyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (tetrahydropyran-4-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (oxetane-3-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (tetrahydrofuran-3-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ acetyl- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (2-methylpropanoyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, TAEGRO (i.e. bacillus amyloliquefaciens strain FZB 24), melaleuca alternifolia oil (melaleuca alternifolia extract (commercially available as Timorex Gold, which is a broad-spectrum plant biological fungicide)), giant knotweed extract (commercially available as REGALIA), a plant extract based on a lycopodium clavatum extract (commercially available as BOTRISTOP), or aureobasidin a, wherein the weight ratio of component (a) to component (B) is from 15:1 to 1:30.

In another preferred composition according to the invention component (A) is compound number X.11 [5- (2, 4-difluorophenyl) isoxazol-3-yl ] - [ rac- (4S, 7S) -7- (1, 5-dimethylpyrazol-4-yl) -4-methyl-6, 7-dihydro-4H-thieno [3,2-c ] pyridin-5-yl ] methanone, or a salt enantiomer, tautomer, or N-oxide thereof, and component (B) is a compound selected from the group consisting of fluxapyroxad hydroxylamine, benzovindiflupyr, bixafen, fluxapyroxad, isopyrazamide, penthiopyrad, Cyproconazole, boscalid, fluopyram, thiaflufenamide, bixafen, flufenamid, and flufenamid, and the like penflufen, indene penflufen, fluoxastrobin, trifluoracetam, and iprovalicarb, indene pencycuron penflufen, triflumizole, penflufen and the like cyproconazole, difenoconazole, metconazole, penconazole, propiconazole, tebuconazole, difenoconazole, prothioconazole, penconazole, trifloxystrobin, triflumizole, iprovalicarb, quinoline trifloxystrobin, metalaxyl-M, cyprodinil, pyrimethanil, mancozeb, copper compounds (different salts), sulfur, folpet, chlorothalonil, dithianon, Propoxyquinoline, fludioxonil, benzofuranone, fluorothiazolyl pyrithione, trifloxysulfate, alamic acid type benzene-S-methyl, phosphorous acid, cyflufenamid, tricyclazole, N-methoxy-N- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] cyclopropanecarboxamide, N, 2-dimethoxy-N- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] propionamide, 1-methoxy-3-methyl-1- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] urea, 1, 3-dimethoxy-1- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] urea, N- [ (1R) -1-benzyl-3-chloro-1-methyl-but-3-enyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-3-chloro-1-methyl-but-3-enyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1R) -1-benzyl-3, 3-trifluoro-1-methyl-propyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-3, 3-trifluoro-1-methyl-propyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl ] -7, 8-difluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-1, 3-dimethyl-butyl ] -7, 8-difluoro-quinoline-3-carboxamide, 8-fluoro-N- [ (1R) -1- [ (3-fluorophenyl) methyl ] -1, 3-dimethyl-butyl ] quinoline-3-carboxamide, 8-fluoro-N- [ (1S) -1- [ (3-fluorophenyl) methyl ] -1, 3-dimethyl-butyl ] quinoline-3-carboxamide, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, N- ((1R) -1-benzyl-3-chloro-1-methyl-but-3-enyl) -8-fluoro-quinoline-3-carboxamide, N- ((1S) -1-benzyl-3-chloro-1-methyl-but-3-enyl) -8-fluoro-quinoline-3-carboxamide, (Z) -3-methoxy-2- [ 2-methyl-5- [4- (trifluoromethyl) triazol-2-yl ] phenoxy ] prop-2-enoic acid methyl ester, (Z) -3-methoxy-2- [ 2-methyl-5- (4-propyltriazol-2-yl) phenoxy ] prop-2-enoic acid methyl ester, (Z) -2- [5- (3-isopropylpyrazol-1-yl) -2-methyl-phenoxy ] -3-methoxy-prop-2-enoic acid methyl ester, Methyl (Z) -3-methoxy-2- [ 2-methyl-5- (3-propylpyrazol-1-yl) phenoxy ] prop-2-enoate, methyl (Z) -3-methoxy-2- [ 2-methyl-5- [3- (trifluoromethyl) pyrazol-1-yl ] phenoxy ] prop-2-enoate, methyl (Z) -2- (5-cyclohexyl-2-methyl-phenoxy) -3-methoxy-prop-2-enoate, methyl (Z) -2- (5-cyclopentyl-2-methyl-phenoxy) -3-methoxy-prop-2-enoate (these compounds can be prepared by the methods described in WO 2020/193387), methyl (Z) -3-methoxy-prop-2-enoate, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -5-methyl-N-spiro [3.4] oct-3-yl-thiazole-4-carboxamide, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -N-hexyl-5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (2-methoxyacetyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (tetrahydropyran-4-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (oxetane-3-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (tetrahydrofuran-3-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ acetyl- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (2-methylpropanoyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, TAEGRO (i.e. bacillus amyloliquefaciens strain FZB 24), melaleuca alternifolia oil (melaleuca alternifolia extract (commercially available as Timorex Gold, which is a broad-spectrum plant biological fungicide)), giant knotweed extract (commercially available as REGALIA), a plant extract based on a lycopodium clavatum extract (commercially available as BOTRISTOP), or aureobasidin a, wherein the weight ratio of component (a) to component (B) is from 15:1 to 1:30.

In still more preferred compositions according to the invention, component (a) is compound number x.01: [5- (2, 4-difluorophenyl) -1,3, 4-thiadiazol-2-yl ] - [ (4R, 7S) -4, 7-dimethyl-4- (1-methylpyrazol-4-yl) -5, 7-dihydrothieno [2,3-c ] pyridin-6-yl ] methanone (X.01), or a salt enantiomer, tautomer, or N-oxide thereof, and component (B) is a compound selected from the group consisting of fluxazoyl hydroxylamine, benzovinfluxazole, azoxystrobin, picolinamide, difenoconazole, prothioconazole, haloxypyr, cyprodinil, fludioxonil, alamic acid-type benzene-S-methyl, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, 2- [2, 6-difluoro-pyridin-4-yl ] -4-carbamide, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (tetrahydropyran-4-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ acetyl- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, TAEGRO @ (i.e. bacillus amyloliquefaciens strain FZB 24), melaleuca alternifolia oil (tea plant melaleuca extract (commercially available as Timorex Gold @, which is a broad-spectrum plant biological fungicide)), giant knotweed extract (commercially available as REGALIA @), a plant extract based on a lycopodium extract (commercially available as BOTRISTOP @), or aurin a, wherein the weight ratio of component (a) to component (B) is from 1 to 30:30.

In another still more preferred composition according to the present invention, component (A) is compound number X.02- [5- (2, 4-difluorophenyl) isoxazol-3-yl ] - [ rac- (4S, 7R) -4, 7-dimethyl-4- (1-methylpyrazol-4-yl) -5, 7-dihydrothieno [2,3-c ] pyridin-6-yl ] methanone (X.02), or a salt enantiomer, tautomer, or N-oxide thereof, and component (B) is a compound selected from the group consisting of fluxazoyl hydroxylamine, benzovindiflupyr, azoxystrobin, picolinide, difenoconazole, prothioconazole, triflumizole, fludioxonil, arabino-benzene-S-methyl, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-3-dimethyl-3-butyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-difluoro-3-methyl-3-2-fluoro-4-cyano-2-fluoro-butanamide, 3-fluoro-2-fluoro-methyl-3-yl ] -N-fluoro-4-fluoro-methyl-4-fluoro-2-fluoro-methyl-2-fluoro-methyl 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (tetrahydropyran-4-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ acetyl- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, TAEGRO @ (i.e. bacillus amyloliquefaciens strain FZB 24), melaleuca alternifolia oil (tea plant melaleuca extract (commercially available as Timorex Gold @, which is a broad-spectrum plant biological fungicide)), giant knotweed extract (commercially available as REGALIA @), a plant extract based on a lycopodium extract (commercially available as BOTRISTOP @), or aurin a, wherein the weight ratio of component (a) to component (B) is from 1 to 30:30.

In another still more preferred composition according to the invention component (A) is compound number X.03- [5- (2, 4-difluorophenyl) isoxazol-3-yl ] - [ rac- (4R, 7S) -7-methyl-4- (1-methylpyrazol-4-yl) -5, 7-dihydro-4H-thieno [2,3-c ] pyridin-6-yl ] methanone (X.03), or a salt enantiomer, tautomer, or N-oxide thereof, and component (B) is a compound selected from the group consisting of fluxazoyl hydroxylamine, benzovinfluxazole, azoxystrobin, picolinide, difenoconazole, prothioconazole, triflumizole, fludioxonil, arabino-benzene-S-methyl, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-3-dimethyl-3-butyl ] -3-carboxamide, N- [ (1S) -1-difluoro-3-methyl-3-2-fluoro-4-cyano-2-fluoro-2-methyl-4-N-3-oxolinide, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (tetrahydropyran-4-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ acetyl- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, TAEGRO @ (i.e. bacillus amyloliquefaciens strain FZB 24), melaleuca alternifolia oil (tea plant melaleuca extract (commercially available as Timorex Gold @, which is a broad-spectrum plant biological fungicide)), giant knotweed extract (commercially available as REGALIA @), a plant extract based on a lycopodium extract (commercially available as BOTRISTOP @), or aurin a, wherein the weight ratio of component (a) to component (B) is from 1 to 30:30.

In another still more preferred composition according to the invention component (A) is compound number X.04, [5- (2, 4-difluorophenyl) -1,3, 4-thiadiazol-2-yl ] - [ rac- (4R, 7S) -7-methyl-4- (1-methylpyrazol-4-yl) -5, 7-dihydro-4H-thieno [2,3-c ] pyridin-6-yl ] methanone (X.04), or a salt enantiomer, tautomer, or N-oxide thereof, and component (B) is a compound selected from the group consisting of fluxazoxazin, benzovinfluxazole, azoxystrobin, picolinamide, difenoconazole, prothioconazole, penfluquin, cyprodinil, fludioxonil, arabino-benzene-S-methyl, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinolin-3-carboxamide, N- [ (1-S) -1-benzyl-3-difluoro-3-methyl ] -3-quinolinyl, N-1- [ (3-fluoro-1, 3-fluoro-4-methyl ] -2-yl ] 2-fluoro-2-yl-fluxazin-3-yl ] -2-yl-fluxazin-3-yl-methyl-4-N-yl-2-yl-fluxazin-yl-2-yl 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (tetrahydropyran-4-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ acetyl- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, TAEGRO @ (i.e. bacillus amyloliquefaciens strain FZB 24), melaleuca alternifolia oil (tea plant melaleuca extract (commercially available as Timorex Gold @, which is a broad-spectrum plant biological fungicide)), giant knotweed extract (commercially available as REGALIA @), a plant extract based on a lycopodium extract (commercially available as BOTRISTOP @), or aurin a, wherein the weight ratio of component (a) to component (B) is from 1 to 30:30.

In another still more preferred composition according to the invention component (A) is compound number X.05, [5- (2, 4-difluorophenyl) -1,3, 4-thiadiazol-2-yl ] - [ 4-methyl-4- (1-methylpyrazol-4-yl) -5, 7-dihydrothieno [2,3-c ] pyridin-6-yl ] methanone (X.05), or a salt enantiomer, tautomer, or N-oxide thereof, and component (B) is a compound selected from the group consisting of fluxazoxamide, benzovindiflupyr, azoxystrobin, picolinide, difenoconazole, prothioconazole, halofop-butyl, cyprodinil, fludioxonil, an arabino-benzene-S-methyl, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-dimethyl-8-fluoro-3-fluoro-quinoline, N- [ 2-fluoro-4-cyano ] -2-fluoro-4-methylbenzamide, 5-fluoro-2-yl ] -N-fluoro-4-carboxamide 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (tetrahydropyran-4-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ acetyl- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, TAEGRO @ (i.e. bacillus amyloliquefaciens strain FZB 24), melaleuca alternifolia oil (tea plant melaleuca extract (commercially available as Timorex Gold @, which is a broad-spectrum plant biological fungicide)), giant knotweed extract (commercially available as REGALIA @), a plant extract based on a lycopodium extract (commercially available as BOTRISTOP @), or aurin a, wherein the weight ratio of component (a) to component (B) is from 1 to 30:30.

In another still more preferred composition according to the invention component (A) is compound number X.06, [5- (2, 4-difluorophenyl) isoxazol-3-yl ] - [ 4-methyl-4- (1-methylpyrazol-4-yl) -5, 7-dihydrothieno [2,3-c ] pyridin-6-yl ] methanone (X.06), or a salt enantiomer, tautomer, or N-oxide thereof, and component (B) is a compound selected from the group consisting of fluxazoxamide, benzovindiflupyr, azoxystrobin, picolinamide, difenoconazole, prothioconazole, penflufen, cyprodinil, fludioxonil, arabino-benzene-S-methyl, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, N- [ 2- (4-fluoro-cyano ] -3-tetramethyl-3-carboxamide, N- [ 4-fluoro-cyano ] -4-tetramethyl-3-carboxamide, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (tetrahydropyran-4-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ acetyl- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, TAEGRO @ (i.e. bacillus amyloliquefaciens strain FZB 24), melaleuca alternifolia oil (tea plant melaleuca extract (commercially available as Timorex Gold @, which is a broad-spectrum plant biological fungicide)), giant knotweed extract (commercially available as REGALIA @), a plant extract based on a lycopodium extract (commercially available as BOTRISTOP @), or aurin a, wherein the weight ratio of component (a) to component (B) is from 1 to 30:30.

In another still more preferred composition according to the invention component (A) is compound number X.07, [5- (2, 4-difluorophenyl) isoxazol-3-yl ] - [ 7-methyl-7- (1-methylpyrazol-4-yl) -4, 6-dihydrothieno [3,2-c ] pyridin-5-yl ] methanone (X.07), or a salt enantiomer, tautomer, or N-oxide thereof, and component (B) is a compound selected from the group consisting of fluxazoxamide, benzovindiflupyr, azoxystrobin, picolinamide, difenoconazole, prothioconazole, penflufen, cyprodinil, fludioxonil, arabino-benzene-S-methyl, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, N- [ 2- (4-fluoro-cyano ] -3-tetramethyl-3-carboxamide, N- [ 4-fluoro-cyano ] -3-tetramethyl-3-carboxamide, 2- [ 4-fluoro-phenyl ] -3-carboxamide, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (tetrahydropyran-4-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ acetyl- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, TAEGRO @ (i.e. bacillus amyloliquefaciens strain FZB 24), melaleuca alternifolia oil (tea plant melaleuca extract (commercially available as Timorex Gold @, which is a broad-spectrum plant biological fungicide)), giant knotweed extract (commercially available as REGALIA @), a plant extract based on a lycopodium extract (commercially available as BOTRISTOP @), or aurin a, wherein the weight ratio of component (a) to component (B) is from 1 to 30:30.

In another still more preferred composition according to the invention component (A) is compound number X.08, [5- (2, 4-difluorophenyl) isoxazol-3-yl ] - [4- (1-methylpyrazol-4-yl) -5, 7-dihydro-4H-isothiazolo [5,4-c ] pyridin-6-yl ] methanone (X.08), or a salt enantiomer, tautomer, or N-oxide thereof, and component (B) is a compound selected from the group consisting of fluxazoxamide, benzovindiflupyr, azoxystrobin, picolinamide, difenoconazole, prothioconazole, penflufen, cyprodinil, fludioxonil, the arabino-benzene-S-methyl, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-3-fluoro-quinoline-3-carboxamide, N- [ 2- (4-cyano-4-tetramethyl-3-carboxamide, N- [ 2-fluoro-phenyl ] -3-carboxamide, N- [ (1S) -1-benzyl-8-fluoro-quinolin-3-carboxamide, N- [ 4-fluoro-methyl ] -3-cyano ] -3-carboxamide, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (tetrahydropyran-4-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ acetyl- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, TAEGRO @ (i.e. bacillus amyloliquefaciens strain FZB 24), melaleuca alternifolia oil (tea plant melaleuca extract (commercially available as Timorex Gold @, which is a broad-spectrum plant biological fungicide)), giant knotweed extract (commercially available as REGALIA @), a plant extract based on a lycopodium extract (commercially available as BOTRISTOP @), or aurin a, wherein the weight ratio of component (a) to component (B) is from 1 to 30:30.

In another still more preferred composition according to the invention component (A) is compound number X.09, [5- (2, 4-difluorophenyl) isoxazol-3-yl ] - [7- (1, 5-dimethylpyrazol-4-yl) -6, 7-dihydro-4H-thiadiazolo [4,5-c ] pyridin-5-yl ] methanone (X.09), or a salt enantiomer, tautomer, or N-oxide thereof, and component (B) is a compound selected from the group consisting of fluxazoxamide, benzovindiflupyr, azoxystrobin, picolinide, difenoconazole, prothioconazole, halofop-butyl, cyprodinil, fludioxonil, arabino-benzene-S-methyl, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-dimethyl-3-fluoro-8-fluoro-quinoline-3-carboxamide, N- [ 2-fluoro-4-cyano ] -2-spiro-4-carboxamide, N- [ 2-fluoro-3-methyl ] -2-cyano-2-oxamide 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (tetrahydropyran-4-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ acetyl- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, TAEGRO @ (i.e. bacillus amyloliquefaciens strain FZB 24), melaleuca alternifolia oil (tea plant melaleuca extract (commercially available as Timorex Gold @, which is a broad-spectrum plant biological fungicide)), giant knotweed extract (commercially available as REGALIA @), a plant extract based on a lycopodium extract (commercially available as BOTRISTOP @), or aurin a, wherein the weight ratio of component (a) to component (B) is from 1 to 30:30.

In another still more preferred composition according to the invention component (A) is compound number X.10, [5- (2, 4-difluorophenyl) isoxazol-3-yl ] - [7- (1, 5-dimethylpyrazol-4-yl) -6, 7-dihydro-4H-thieno [3,2-c ] pyridin-5-yl ] methanone (X.10), or a salt enantiomer, tautomer, or N-oxide thereof, and component (B) is a compound selected from the group consisting of fluxazoxamide, benzovindiflupyr, azoxystrobin, picolinamide, difenoconazole, prothioconazole, difenoconazole, cyprodinil, fludioxonil, alamic acid-type benzene-S-methyl, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-1, 3-dimethyl-8-fluoro-3-quinoline-3-fluoro-3-carboxamide, N- [ 2-fluoro-4-cyano ] -4-spiro-carboxamide, N- [ 4-fluoro-3-carboxamide, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (tetrahydropyran-4-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ acetyl- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, TAEGRO @ (i.e. bacillus amyloliquefaciens strain FZB 24), melaleuca alternifolia oil (tea plant melaleuca extract (commercially available as Timorex Gold @, which is a broad-spectrum plant biological fungicide)), giant knotweed extract (commercially available as REGALIA @), a plant extract based on a lycopodium extract (commercially available as BOTRISTOP @), or aurin a, wherein the weight ratio of component (a) to component (B) is from 1 to 30:30.

In another still more preferred composition according to the present invention, component (A) is compound number X.11- [5- (2, 4-difluorophenyl) isoxazol-3-yl ] - [ rac- (4S, 7S) -7- (1, 5-dimethylpyrazole-4-yl) -4-methyl-6, 7-dihydro-4H-thieno [3,2-c ] pyridin-5-yl ] methanone, or a salt enantiomer, tautomer, or N-oxide thereof, and component (B) is a compound selected from the group consisting of fluxazoyl hydroxylamine, benzovindiflupyr, azoxystrobin, picolinide, difenoconazole, prothioconazole, triflumizole, fludioxonil, arabino-benzene-S-methyl, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-3-dimethyl-3-butyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-difluoro-3-methyl-3-2-fluoro-4-cyano-2-fluoro-butanamide, 3-fluoro-2-fluoro-methyl-3-yl-N-yl-fluoro-2-fluoro-methyl-2-fluoro-1-methyl 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (tetrahydropyran-4-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ acetyl- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, TAEGRO @ (i.e. bacillus amyloliquefaciens strain FZB 24), melaleuca alternifolia oil (tea plant melaleuca extract (commercially available as Timorex Gold @, which is a broad-spectrum plant biological fungicide)), giant knotweed extract (commercially available as REGALIA @), a plant extract based on a lycopodium extract (commercially available as BOTRISTOP @), or aurin a, wherein the weight ratio of component (a) to component (B) is from 1 to 30:30.

In still more preferred compositions according to the invention component (A) is compound number X.01, [5- (2, 4-difluorophenyl) -1,3, 4-thiadiazol-2-yl ] - [ (4R, 7S) -4, 7-dimethyl-4- (1-methylpyrazol-4-yl) -5, 7-dihydrothieno [2,3-c ] pyridin-6-yl ] methanone (X.01), or a salt enantiomer, tautomer, or N-oxide thereof, and component (B) is a compound selected from the group consisting of fluxapyroxal, benzovindiflupyr, bixafen, fluxapyroxad, isopyrazam, Triflumamid, pyraclostrobin, trifloxystrobin azoxystrobin, tetrazolidone triflumamid, pyraclostrobin, trifloxystrobin, azoxystrobin, tetrazolidone picolide, picolinamide, fluazinam, fenpropidin fenhexamid, cyproconazole, difenoconazole, metconazole, penconazole, propiconazole, tebuconazole, penconazole, prothioconazole, penconazole, triflumizole, iprovalicarb, triflumuron, metalaxyl-M, cyprodinil, pyrimethanil, mancozeb, copper compounds (different salts), sulfur, folpet, chlorothalonil, Dithianon, propoxyquinoline, fludioxonil, phenomenone, fluorothiazolyl ethanone, trifloxysulphate, alamic acid type benzene-S-methyl, phosphorous acid, cyclophosphamide, tricyclazole, N-methoxy-N- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] cyclopropanecarboxamide, N, 2-dimethoxy-N- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] propionamide, 1-methoxy-3-methyl-1- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] urea, 1, 3-dimethoxy-1- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] urea, N- [ (1R) -1-benzyl-3-chloro-1-methyl-but-3-enyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-3-chloro-1-methyl-but-3-enyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1R) -1-benzyl-3, 3-trifluoro-1-methyl-propyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-3, 3-trifluoro-1-methyl-propyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl ] -7, 8-difluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-1, 3-dimethyl-butyl ] -7, 8-difluoro-quinoline-3-carboxamide, 8-fluoro-N- [ (1R) -1- [ (3-fluorophenyl) methyl ] -1, 3-dimethyl-butyl ] quinoline-3-carboxamide, 8-fluoro-N- [ (1S) -1- [ (3-fluorophenyl) methyl ] -1, 3-dimethyl-butyl ] quinoline-3-carboxamide, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, N- ((1R) -1-benzyl-3-chloro-1-methyl-but-3-enyl) -8-fluoro-quinoline-3-carboxamide, N- ((1S) -1-benzyl-3-chloro-1-methyl-but-3-enyl) -8-fluoro-quinoline-3-carboxamide, (Z) -3-methoxy-2- [ 2-methyl-5- [4- (trifluoromethyl) triazol-2-yl ] phenoxy ] prop-2-enoic acid methyl ester, (Z) -3-methoxy-2- [ 2-methyl-5- (4-propyltriazol-2-yl) phenoxy ] prop-2-enoic acid methyl ester, (Z) -2- [5- (3-Isopropylpyrazol-1-yl) -2-methyl-phenoxy ] -3-methoxy-prop-2-enoic acid methyl ester, (Z) -3-methoxy-2- [ 2-methyl-5- (3-propylpyrazol-1-yl) phenoxy ] prop-2-enoic acid methyl ester, (Z) -3-methoxy-2- [ 2-methyl-5- [3- (trifluoromethyl) pyrazol-1-yl ] phenoxy ] prop-2-enoic acid methyl ester, (Z) -2- (5-cyclohexyl-2-methyl-phenoxy) -3-methoxy-prop-2-enoic acid methyl ester, (Z) -2- (5-cyclopentyl-2-methyl-phenoxy) -3-methoxy-prop-2-enoic acid methyl ester (these compounds can be prepared by the methods described in WO 2020/193387), 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -5-methyl-N-spiro [3.4] oct-3-yl-thiazole-4-carboxamide, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -N-hexyl-5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (2-methoxyacetyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (tetrahydropyran-4-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (oxetane-3-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (tetrahydrofuran-3-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ acetyl- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (2-methylpropanoyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, TAEGRO (i.e. bacillus amyloliquefaciens strain FZB 24), melaleuca alternifolia oil (melaleuca alternifolia extract (commercially available as Timorex Gold, which is a broad spectrum plant biological fungicide)), giant knotweed extract (commercially available as REGALIA), a plant extract based on a lycopodium clavatum extract (commercially available as BOTRISTOP), or aureobasidin a, wherein the weight ratio of component (a) to component (B) is from 10:1 to 1:10 (or even more preferably, 5:1 to 1:5).

In another still more preferred composition according to the invention, component (A) is compound number X.02 [5- (2, 4-difluorophenyl) isoxazol-3-yl ] - [ rac- (4S, 7R) -4, 7-dimethyl-4- (1-methylpyrazol-4-yl) -5, 7-dihydrothieno [2,3-c ] pyridin-6-yl ] methanone (X.02), or a salt enantiomer, tautomer, or N-oxide thereof, and component (B) is a compound selected from the group consisting of fluxapyroxal hydroxylamine, benzovindiflupyr, bixafen, fluxapyroxad, isopyrazamate, Triflumamid, pyraclostrobin, trifloxystrobin azoxystrobin, tetrazolidone triflumamid, pyraclostrobin, trifloxystrobin, azoxystrobin, tetrazolidone picolide, picolinamide, fluazinam, fenpropidin fenhexamid, cyproconazole, difenoconazole, metconazole, penconazole, propiconazole, tebuconazole, penconazole, prothioconazole, penconazole, triflumizole, iprovalicarb, triflumuron, metalaxyl-M, cyprodinil, pyrimethanil, mancozeb, copper compounds (different salts), sulfur, folpet, chlorothalonil, Dithianon, propoxyquinoline, fludioxonil, phenomenone, fluorothiazolyl ethanone, trifloxysulphate, alamic acid type benzene-S-methyl, phosphorous acid, cyclophosphamide, tricyclazole, N-methoxy-N- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] cyclopropanecarboxamide, N, 2-dimethoxy-N- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] propionamide, 1-methoxy-3-methyl-1- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] urea, 1, 3-dimethoxy-1- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] urea, N- [ (1R) -1-benzyl-3-chloro-1-methyl-but-3-enyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-3-chloro-1-methyl-but-3-enyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1R) -1-benzyl-3, 3-trifluoro-1-methyl-propyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-3, 3-trifluoro-1-methyl-propyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl ] -7, 8-difluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-1, 3-dimethyl-butyl ] -7, 8-difluoro-quinoline-3-carboxamide, 8-fluoro-N- [ (1R) -1- [ (3-fluorophenyl) methyl ] -1, 3-dimethyl-butyl ] quinoline-3-carboxamide, 8-fluoro-N- [ (1S) -1- [ (3-fluorophenyl) methyl ] -1, 3-dimethyl-butyl ] quinoline-3-carboxamide, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, N- ((1R) -1-benzyl-3-chloro-1-methyl-but-3-enyl) -8-fluoro-quinoline-3-carboxamide, N- ((1S) -1-benzyl-3-chloro-1-methyl-but-3-enyl) -8-fluoro-quinoline-3-carboxamide, (Z) -3-methoxy-2- [ 2-methyl-5- [4- (trifluoromethyl) triazol-2-yl ] phenoxy ] prop-2-enoic acid methyl ester, (Z) -3-methoxy-2- [ 2-methyl-5- (4-propyltriazol-2-yl) phenoxy ] prop-2-enoic acid methyl ester, (Z) -2- [5- (3-Isopropylpyrazol-1-yl) -2-methyl-phenoxy ] -3-methoxy-prop-2-enoic acid methyl ester, (Z) -3-methoxy-2- [ 2-methyl-5- (3-propylpyrazol-1-yl) phenoxy ] prop-2-enoic acid methyl ester, (Z) -3-methoxy-2- [ 2-methyl-5- [3- (trifluoromethyl) pyrazol-1-yl ] phenoxy ] prop-2-enoic acid methyl ester, (Z) -2- (5-cyclohexyl-2-methyl-phenoxy) -3-methoxy-prop-2-enoic acid methyl ester, (Z) -2- (5-cyclopentyl-2-methyl-phenoxy) -3-methoxy-prop-2-enoic acid methyl ester (these compounds can be prepared by the methods described in WO 2020/193387), 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -5-methyl-N-spiro [3.4] oct-3-yl-thiazole-4-carboxamide, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -N-hexyl-5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (2-methoxyacetyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (tetrahydropyran-4-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (oxetane-3-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (tetrahydrofuran-3-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ acetyl- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (2-methylpropanoyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, TAEGRO (i.e. bacillus amyloliquefaciens strain FZB 24), melaleuca alternifolia oil (melaleuca alternifolia extract (commercially available as Timorex Gold, which is a broad spectrum plant biological fungicide)), giant knotweed extract (commercially available as REGALIA), a plant extract based on a lycopodium clavatum extract (commercially available as BOTRISTOP), or aureobasidin a, wherein the weight ratio of component (a) to component (B) is from 10:1 to 1:10 (or even more preferably, 5:1 to 1:5).

In another still more preferred composition according to the invention, component (A) is compound number X.03 [5- (2, 4-difluorophenyl) isoxazol-3-yl ] - [ rac- (4R, 7S) -7-methyl-4- (1-methylpyrazol-4-yl) -5, 7-dihydro-4H-thieno [2,3-c ] pyridin-6-yl ] methanone (X.03), or a salt enantiomer, tautomer, or N-oxide thereof, and component (B) is a compound selected from the group consisting of fluxapyroxal hydroxylamine, benzovindiflupyr, bixafen, fluxapyroxad, isopyrazam, Triflumamid, pyraclostrobin, trifloxystrobin azoxystrobin, tetrazolidone triflumamid, pyraclostrobin, trifloxystrobin, azoxystrobin, tetrazolidone picolide, picolinamide, fluazinam, fenpropidin fenhexamid, cyproconazole, difenoconazole, metconazole, penconazole, propiconazole, tebuconazole, penconazole, prothioconazole, penconazole, triflumizole, iprovalicarb, triflumuron, metalaxyl-M, cyprodinil, pyrimethanil, mancozeb, copper compounds (different salts), sulfur, folpet, chlorothalonil, Dithianon, propoxyquinoline, fludioxonil, phenomenone, fluorothiazolyl ethanone, trifloxysulphate, alamic acid type benzene-S-methyl, phosphorous acid, cyclophosphamide, tricyclazole, N-methoxy-N- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] cyclopropanecarboxamide, N, 2-dimethoxy-N- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] propionamide, 1-methoxy-3-methyl-1- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] urea, 1, 3-dimethoxy-1- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] urea, N- [ (1R) -1-benzyl-3-chloro-1-methyl-but-3-enyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-3-chloro-1-methyl-but-3-enyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1R) -1-benzyl-3, 3-trifluoro-1-methyl-propyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-3, 3-trifluoro-1-methyl-propyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl ] -7, 8-difluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-1, 3-dimethyl-butyl ] -7, 8-difluoro-quinoline-3-carboxamide, 8-fluoro-N- [ (1R) -1- [ (3-fluorophenyl) methyl ] -1, 3-dimethyl-butyl ] quinoline-3-carboxamide, 8-fluoro-N- [ (1S) -1- [ (3-fluorophenyl) methyl ] -1, 3-dimethyl-butyl ] quinoline-3-carboxamide, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, N- ((1R) -1-benzyl-3-chloro-1-methyl-but-3-enyl) -8-fluoro-quinoline-3-carboxamide, N- ((1S) -1-benzyl-3-chloro-1-methyl-but-3-enyl) -8-fluoro-quinoline-3-carboxamide, (Z) -3-methoxy-2- [ 2-methyl-5- [4- (trifluoromethyl) triazol-2-yl ] phenoxy ] prop-2-enoic acid methyl ester, (Z) -3-methoxy-2- [ 2-methyl-5- (4-propyltriazol-2-yl) phenoxy ] prop-2-enoic acid methyl ester, (Z) -2- [5- (3-Isopropylpyrazol-1-yl) -2-methyl-phenoxy ] -3-methoxy-prop-2-enoic acid methyl ester, (Z) -3-methoxy-2- [ 2-methyl-5- (3-propylpyrazol-1-yl) phenoxy ] prop-2-enoic acid methyl ester, (Z) -3-methoxy-2- [ 2-methyl-5- [3- (trifluoromethyl) pyrazol-1-yl ] phenoxy ] prop-2-enoic acid methyl ester, (Z) -2- (5-cyclohexyl-2-methyl-phenoxy) -3-methoxy-prop-2-enoic acid methyl ester, (Z) -2- (5-cyclopentyl-2-methyl-phenoxy) -3-methoxy-prop-2-enoic acid methyl ester (these compounds can be prepared by the methods described in WO 2020/193387), 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -5-methyl-N-spiro [3.4] oct-3-yl-thiazole-4-carboxamide, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -N-hexyl-5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (2-methoxyacetyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (tetrahydropyran-4-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (oxetane-3-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (tetrahydrofuran-3-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ acetyl- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (2-methylpropanoyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, TAEGRO (i.e. bacillus amyloliquefaciens strain FZB 24), melaleuca alternifolia oil (melaleuca alternifolia extract (commercially available as Timorex Gold, which is a broad spectrum plant biological fungicide)), giant knotweed extract (commercially available as REGALIA), a plant extract based on a lycopodium clavatum extract (commercially available as BOTRISTOP), or aureobasidin a, wherein the weight ratio of component (a) to component (B) is from 10:1 to 1:10 (or even more preferably, 5:1 to 1:5).

In another still more preferred composition according to the invention, component (A) is compound number X.04, [5- (2, 4-difluorophenyl) -1,3, 4-thiadiazol-2-yl ] - [ rac- (4R, 7S) -7-methyl-4- (1-methylpyrazol-4-yl) -5, 7-dihydro-4H-thieno [2,3-c ] pyridin-6-yl ] methanone (X.04), or a salt enantiomer, tautomer, or N-oxide thereof, and component (B) is a compound selected from the group consisting of fluxapyroxal hydroxylamine, benzovindiflupyr, bixafen, fluxapyroxad, Isopyrazam, penthiopyrad, cyproconazole, boscalid, fluopyram, flupyraclostrobin, fluxapyroxad, fluxad, and the like thiaflufenamide, bixafen, ipflupyraclostrobin, indene picolinamine thiaflufenamide, bixafen, and other drugs iprovalicarb, indene pencycuron fenpropidin, cyproconazole, difenoconazole, metconazole, penconazole, cyproconazole, difenoconazole, metconazole, difenoconazole, metconazole propiconazole, tebuconazole, fluoroether azole, prothioconazole, penconazole, difenoconazole triflumizole, iprodione, triflumuron, metalaxyl-M, cyprodinil, pyrimethanil, mancozeb, copper compounds (different salts), sulfur, Folpet, chlorothalonil, dithianon, propoxyquinoline, fludioxonil, phenomenon, fluorothiazolyl ethanone, fluorooxamate sulphonyl, alamic acid type benzene-S-methyl, phosphorous acid, cyflufenamid, tricyclazole, N-methoxy-N- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] cyclopropanecarboxamide, N, 2-dimethoxy-N- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] propionamide, 1-methoxy-3-methyl-1- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] urea, 1, 3-dimethoxy-1- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] urea, N- [ (1R) -1-benzyl-3-chloro-1-methyl-but-3-enyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-3-chloro-1-methyl-but-3-enyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1R) -1-benzyl-3, 3-trifluoro-1-methyl-propyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-3, 3-trifluoro-1-methyl-propyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl ] -7, 8-difluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-1, 3-dimethyl-butyl ] -7, 8-difluoro-quinoline-3-carboxamide, 8-fluoro-N- [ (1R) -1- [ (3-fluorophenyl) methyl ] -1, 3-dimethyl-butyl ] quinoline-3-carboxamide, 8-fluoro-N- [ (1S) -1- [ (3-fluorophenyl) methyl ] -1, 3-dimethyl-butyl ] quinoline-3-carboxamide, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, N- ((1R) -1-benzyl-3-chloro-1-methyl-but-3-enyl) -8-fluoro-quinoline-3-carboxamide, N- ((1S) -1-benzyl-3-chloro-1-methyl-but-3-enyl) -8-fluoro-quinoline-3-carboxamide, (Z) -3-methoxy-2- [ 2-methyl-5- [4- (trifluoromethyl) triazol-2-yl ] phenoxy ] prop-2-enoic acid methyl ester, (Z) -3-methoxy-2- [ 2-methyl-5- (4-propyltriazol-2-yl) phenoxy ] prop-2-enoic acid methyl ester, (Z) -2- [5- (3-Isopropylpyrazol-1-yl) -2-methyl-phenoxy ] -3-methoxy-prop-2-enoic acid methyl ester, (Z) -3-methoxy-2- [ 2-methyl-5- (3-propylpyrazol-1-yl) phenoxy ] prop-2-enoic acid methyl ester, (Z) -3-methoxy-2- [ 2-methyl-5- [3- (trifluoromethyl) pyrazol-1-yl ] phenoxy ] prop-2-enoic acid methyl ester, (Z) -2- (5-cyclohexyl-2-methyl-phenoxy) -3-methoxy-prop-2-enoic acid methyl ester, (Z) -2- (5-cyclopentyl-2-methyl-phenoxy) -3-methoxy-prop-2-enoic acid methyl ester (these compounds can be prepared by the methods described in WO 2020/193387), 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -5-methyl-N-spiro [3.4] oct-3-yl-thiazole-4-carboxamide, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -N-hexyl-5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (2-methoxyacetyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (tetrahydropyran-4-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (oxetane-3-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (tetrahydrofuran-3-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ acetyl- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (2-methylpropanoyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, TAEGRO (i.e. bacillus amyloliquefaciens strain FZB 24), melaleuca alternifolia oil (melaleuca alternifolia extract (commercially available as Timorex Gold, which is a broad spectrum plant biological fungicide)), giant knotweed extract (commercially available as REGALIA), a plant extract based on a lycopodium clavatum extract (commercially available as BOTRISTOP), or aureobasidin a, wherein the weight ratio of component (a) to component (B) is from 10:1 to 1:10 (or even more preferably, 5:1 to 1:5).

In another still more preferred composition according to the invention, component (A) is compound number X.05, [5- (2, 4-difluorophenyl) -1,3, 4-thiadiazol-2-yl ] - [ 4-methyl-4- (1-methylpyrazol-4-yl) -5, 7-dihydrothieno [2,3-c ] pyridin-6-yl ] methanone (X.05), or a salt enantiomer, tautomer, or N-oxide thereof, and component (B) is a compound selected from the group consisting of fluxapyroxad hydroxylamine, benzovindiflupyr, bipyramid, fluxapyroxad, isopyrazam, penthiopyrad, fluxapyroxad, epoxiconamine, Trifloxystrobin, azoxystrobin, tetrazolidone picolide, picolinamide trifloxystrobin, azoxystrobin, tetrazolidone, picolide, picolinamide, trifloxystrobin, picolinamide, and pyrad hoc, or mixtures thereof Pyridinamide, fluazinam, fenpropidin, cyproconazole difenoconazole, metconazole, penconazole, propiconazole, tebuconazole, penconazole, prothioconazole, penoxsulam, triflumizole, triflumuron, iprovalicarb, triflumuron, metalaxyl-M, cyprodinil, pyrimethanil, mancozeb, copper compounds (different salts), sulfur, folpet, chlorothalonil, dithianon, propioquinoline, trifloxystrobin, Fludioxonil, benzofuranone, fluorothiazolyl ethanone, trifloxysulf, alamic acid type benzene-S-methyl, phosphorous acid, cyflufenamid, tricyclazole, N-methoxy-N- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] cyclopropanecarboxamide, N, 2-dimethoxy-N- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] propionamide, 1-methoxy-3-methyl-1- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] urea, 1, 3-dimethoxy-1- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] urea, N- [ (1R) -1-benzyl-3-chloro-1-methyl-but-3-enyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-3-chloro-1-methyl-but-3-enyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1R) -1-benzyl-3, 3-trifluoro-1-methyl-propyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-3, 3-trifluoro-1-methyl-propyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl ] -7, 8-difluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-1, 3-dimethyl-butyl ] -7, 8-difluoro-quinoline-3-carboxamide, 8-fluoro-N- [ (1R) -1- [ (3-fluorophenyl) methyl ] -1, 3-dimethyl-butyl ] quinoline-3-carboxamide, 8-fluoro-N- [ (1S) -1- [ (3-fluorophenyl) methyl ] -1, 3-dimethyl-butyl ] quinoline-3-carboxamide, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, N- ((1R) -1-benzyl-3-chloro-1-methyl-but-3-enyl) -8-fluoro-quinoline-3-carboxamide, N- ((1S) -1-benzyl-3-chloro-1-methyl-but-3-enyl) -8-fluoro-quinoline-3-carboxamide, (Z) -3-methoxy-2- [ 2-methyl-5- [4- (trifluoromethyl) triazol-2-yl ] phenoxy ] prop-2-enoic acid methyl ester, (Z) -3-methoxy-2- [ 2-methyl-5- (4-propyltriazol-2-yl) phenoxy ] prop-2-enoic acid methyl ester, (Z) -2- [5- (3-isopropylpyrazol-1-yl) -2-methyl-phenoxy ] -3-methoxy-prop-2-enoic acid methyl ester, Methyl (Z) -3-methoxy-2- [ 2-methyl-5- (3-propylpyrazol-1-yl) phenoxy ] prop-2-enoate, methyl (Z) -3-methoxy-2- [ 2-methyl-5- [3- (trifluoromethyl) pyrazol-1-yl ] phenoxy ] prop-2-enoate, methyl (Z) -2- (5-cyclohexyl-2-methyl-phenoxy) -3-methoxy-prop-2-enoate, methyl (Z) -2- (5-cyclopentyl-2-methyl-phenoxy) -3-methoxy-prop-2-enoate (these compounds can be prepared by the methods described in WO 2020/193387), methyl (Z) -3-methoxy-prop-2-enoate, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -5-methyl-N-spiro [3.4] oct-3-yl-thiazole-4-carboxamide, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -N-hexyl-5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (2-methoxyacetyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (tetrahydropyran-4-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (oxetane-3-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (tetrahydrofuran-3-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ acetyl- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (2-methylpropanoyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, TAEGRO (i.e. bacillus amyloliquefaciens strain FZB 24), melaleuca alternifolia oil (melaleuca alternifolia extract (commercially available as Timorex Gold, which is a broad spectrum plant biological fungicide)), giant knotweed extract (commercially available as REGALIA), a plant extract based on a lycopodium clavatum extract (commercially available as BOTRISTOP), or aureobasidin a, wherein the weight ratio of component (a) to component (B) is from 10:1 to 1:10 (or even more preferably, 5:1 to 1:5).

In another still more preferred composition according to the invention, component (A) is compound number X.06: [5- (2, 4-difluorophenyl) isoxazol-3-yl ] - [ 4-methyl-4- (1-methylpyrazol-4-yl) -5, 7-dihydrothieno [2,3-c ] pyridin-6-yl ] methanone (X.06), or a salt enantiomer, tautomer, or N-oxide thereof, and component (B) is a compound selected from the group consisting of fluxapyroxad hydroxylamine, benzovindiflupyr, bixafen, fluxapyroxad, isopyrazam, penthiopyrad, fluxapyroxad, boscalid, fluxad, fluopicolide, thiaflufenamide, bixafen, iprovalicarb, indenopyrazolam, penconazole, triflumamid, pyraclostrobin, trifloxystrobin, azoxystrobin, tetrazolidone, picolide, picolinamide, fluazinam, fenpropidin, fenhexamid, cyproconazole, difenoconazole, trifloxystrobin, fenpropiconazole, fenpropion-methyl, and the like metconazole, penconazole, propiconazole, tebuconazole, penconazole, prothioconazole, penconazole, triflumizole, iprovalicarb, triflumuron, metalaxyl-M, cyprodinil, pyrimethanil, mancozeb, copper compounds (different salts), sulfur, folpet, chlorothalonil, dithianon, propioquinoline, fludioxonil, Benzofuranone, fluorothiazolyl ethanone, fluorooxazamate, alamic acid-benzene-S-methyl, phosphorous acid, cyflufenamid, tricyclazole, N-methoxy-N- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] cyclopropanecarboxamide, N, 2-dimethoxy-N- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] propionamide, 1-methoxy-3-methyl-1- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] urea, 1, 3-dimethoxy-1- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] urea, N- [ (1R) -1-benzyl-3-chloro-1-methyl-but-3-enyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-3-chloro-1-methyl-but-3-enyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1R) -1-benzyl-3, 3-trifluoro-1-methyl-propyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-3, 3-trifluoro-1-methyl-propyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl ] -7, 8-difluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-1, 3-dimethyl-butyl ] -7, 8-difluoro-quinoline-3-carboxamide, 8-fluoro-N- [ (1R) -1- [ (3-fluorophenyl) methyl ] -1, 3-dimethyl-butyl ] quinoline-3-carboxamide, 8-fluoro-N- [ (1S) -1- [ (3-fluorophenyl) methyl ] -1, 3-dimethyl-butyl ] quinoline-3-carboxamide, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, N- ((1R) -1-benzyl-3-chloro-1-methyl-but-3-enyl) -8-fluoro-quinoline-3-carboxamide, N- ((1S) -1-benzyl-3-chloro-1-methyl-but-3-enyl) -8-fluoro-quinoline-3-carboxamide, (Z) -3-methoxy-2- [ 2-methyl-5- [4- (trifluoromethyl) triazol-2-yl ] phenoxy ] prop-2-enoic acid methyl ester, (Z) -3-methoxy-2- [ 2-methyl-5- (4-propyltriazol-2-yl) phenoxy ] prop-2-enoic acid methyl ester, (Z) -2- [5- (3-isopropylpyrazol-1-yl) -2-methyl-phenoxy ] -3-methoxy-prop-2-enoic acid methyl ester, Methyl (Z) -3-methoxy-2- [ 2-methyl-5- (3-propylpyrazol-1-yl) phenoxy ] prop-2-enoate, methyl (Z) -3-methoxy-2- [ 2-methyl-5- [3- (trifluoromethyl) pyrazol-1-yl ] phenoxy ] prop-2-enoate, methyl (Z) -2- (5-cyclohexyl-2-methyl-phenoxy) -3-methoxy-prop-2-enoate, methyl (Z) -2- (5-cyclopentyl-2-methyl-phenoxy) -3-methoxy-prop-2-enoate (these compounds can be prepared by the methods described in WO 2020/193387), methyl (Z) -3-methoxy-prop-2-enoate, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -5-methyl-N-spiro [3.4] oct-3-yl-thiazole-4-carboxamide, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -N-hexyl-5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (2-methoxyacetyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (tetrahydropyran-4-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (oxetane-3-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (tetrahydrofuran-3-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ acetyl- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (2-methylpropanoyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, TAEGRO (i.e. bacillus amyloliquefaciens strain FZB 24), melaleuca alternifolia oil (melaleuca alternifolia extract (commercially available as Timorex Gold, which is a broad spectrum plant biological fungicide)), giant knotweed extract (commercially available as REGALIA), a plant extract based on a lycopodium clavatum extract (commercially available as BOTRISTOP), or aureobasidin a, wherein the weight ratio of component (a) to component (B) is from 10:1 to 1:10 (or even more preferably, 5:1 to 1:5).

In another still more preferred composition according to the invention, component (A) is compound number X.07, [5- (2, 4-difluorophenyl) isoxazol-3-yl ] - [ 7-methyl-7- (1-methylpyrazol-4-yl) -4, 6-dihydrothieno [3,2-c ] pyridin-5-yl ] methanone (X.07), or a salt enantiomer, tautomer, or N-oxide thereof, and component (B) is a compound selected from the group consisting of fluxapyroxad hydroxylamine, benzovindiflupyr, bipyramid, fluxapyroxad, isopyrazam, penthiopyrad, epoxiconamine, boscalid, fluxad, fluopicolide, thiaflufenamide, bixafen, iprovalicarb, indenopyrazolam, penconazole, triflumamid, pyraclostrobin, trifloxystrobin, azoxystrobin, tetrazolidone, picolide, picolinamide, fluazinam, fenpropidin, fenhexamid, cyproconazole, difenoconazole, trifloxystrobin, fenpropiconazole, fenpropion-methyl, and the like metconazole, penconazole, propiconazole, tebuconazole, penconazole, prothioconazole, penconazole, triflumizole, iprovalicarb, triflumuron, metalaxyl-M, cyprodinil, pyrimethanil, mancozeb, copper compounds (different salts), sulfur, folpet, chlorothalonil, dithianon, propioquinoline, fludioxonil, Benzofuranone, fluorothiazolyl ethanone, fluorooxazamate, alamic acid-benzene-S-methyl, phosphorous acid, cyflufenamid, tricyclazole, N-methoxy-N- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] cyclopropanecarboxamide, N, 2-dimethoxy-N- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] propionamide, 1-methoxy-3-methyl-1- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] urea, 1, 3-dimethoxy-1- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] urea, N- [ (1R) -1-benzyl-3-chloro-1-methyl-but-3-enyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-3-chloro-1-methyl-but-3-enyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1R) -1-benzyl-3, 3-trifluoro-1-methyl-propyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-3, 3-trifluoro-1-methyl-propyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl ] -7, 8-difluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-1, 3-dimethyl-butyl ] -7, 8-difluoro-quinoline-3-carboxamide, 8-fluoro-N- [ (1R) -1- [ (3-fluorophenyl) methyl ] -1, 3-dimethyl-butyl ] quinoline-3-carboxamide, 8-fluoro-N- [ (1S) -1- [ (3-fluorophenyl) methyl ] -1, 3-dimethyl-butyl ] quinoline-3-carboxamide, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, N- ((1R) -1-benzyl-3-chloro-1-methyl-but-3-enyl) -8-fluoro-quinoline-3-carboxamide, N- ((1S) -1-benzyl-3-chloro-1-methyl-but-3-enyl) -8-fluoro-quinoline-3-carboxamide, (Z) -3-methoxy-2- [ 2-methyl-5- [4- (trifluoromethyl) triazol-2-yl ] phenoxy ] prop-2-enoic acid methyl ester, (Z) -3-methoxy-2- [ 2-methyl-5- (4-propyltriazol-2-yl) phenoxy ] prop-2-enoic acid methyl ester, (Z) -2- [5- (3-isopropylpyrazol-1-yl) -2-methyl-phenoxy ] -3-methoxy-prop-2-enoic acid methyl ester, Methyl (Z) -3-methoxy-2- [ 2-methyl-5- (3-propylpyrazol-1-yl) phenoxy ] prop-2-enoate, methyl (Z) -3-methoxy-2- [ 2-methyl-5- [3- (trifluoromethyl) pyrazol-1-yl ] phenoxy ] prop-2-enoate, methyl (Z) -2- (5-cyclohexyl-2-methyl-phenoxy) -3-methoxy-prop-2-enoate, methyl (Z) -2- (5-cyclopentyl-2-methyl-phenoxy) -3-methoxy-prop-2-enoate (these compounds can be prepared by the methods described in WO 2020/193387), methyl (Z) -3-methoxy-prop-2-enoate, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -5-methyl-N-spiro [3.4] oct-3-yl-thiazole-4-carboxamide, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -N-hexyl-5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (2-methoxyacetyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (tetrahydropyran-4-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (oxetane-3-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (tetrahydrofuran-3-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ acetyl- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (2-methylpropanoyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, TAEGRO (i.e., bacillus amyloliquefaciens strain FZB 24), melaleuca alternifolia oil (melaleuca alternifolia extract (commercially available as Timorex Gold, which is a broad-spectrum plant biological fungicide)), giant knotweed extract (commercially available as REGALIA), a plant extract based on a lycopodium clavatum extract (commercially available as BOTRISTOP), or aureobasidin a, wherein the weight ratio of component (a) to component (B) is from 10:1 to 1:10 (or even more preferably, 5:1 to 1:5)

In another still more preferred composition according to the invention, component (A) is compound number X.08, [5- (2, 4-difluorophenyl) isoxazol-3-yl ] - [4- (1-methylpyrazol-4-yl) -5, 7-dihydro-4H-isothiazolo [5,4-c ] pyridin-6-yl ] methanone (X.08), or a salt enantiomer, tautomer, or N-oxide thereof, and component (B) is a compound selected from the group consisting of fluxapyroxad hydroxylamine, benzovindiflupyr, bipyramid, fluxapyroxad, isopyrazam, penthiopyrad, epoxiconamine, boscalid, fluxad, fluopicolide, thiaflufenamide, bixafen, iprovalicarb, indenopyrazolam, penconazole, triflumamid, pyraclostrobin, trifloxystrobin, azoxystrobin, tetrazolidone, picolide, picolinamide, fluazinam, fenpropidin, fenhexamid, cyproconazole, difenoconazole, trifloxystrobin, fenpropiconazole, fenpropion-methyl, and the like metconazole, penconazole, propiconazole, tebuconazole, penconazole, prothioconazole, penconazole, triflumizole, iprovalicarb, triflumuron, metalaxyl-M, cyprodinil, pyrimethanil, mancozeb, copper compounds (different salts), sulfur, folpet, chlorothalonil, dithianon, propioquinoline, fludioxonil, Benzofuranone, fluorothiazolyl ethanone, fluorooxazamate, alamic acid-benzene-S-methyl, phosphorous acid, cyflufenamid, tricyclazole, N-methoxy-N- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] cyclopropanecarboxamide, N, 2-dimethoxy-N- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] propionamide, 1-methoxy-3-methyl-1- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] urea, 1, 3-dimethoxy-1- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] urea, N- [ (1R) -1-benzyl-3-chloro-1-methyl-but-3-enyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-3-chloro-1-methyl-but-3-enyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1R) -1-benzyl-3, 3-trifluoro-1-methyl-propyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-3, 3-trifluoro-1-methyl-propyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl ] -7, 8-difluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-1, 3-dimethyl-butyl ] -7, 8-difluoro-quinoline-3-carboxamide, 8-fluoro-N- [ (1R) -1- [ (3-fluorophenyl) methyl ] -1, 3-dimethyl-butyl ] quinoline-3-carboxamide, 8-fluoro-N- [ (1S) -1- [ (3-fluorophenyl) methyl ] -1, 3-dimethyl-butyl ] quinoline-3-carboxamide, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, N- ((1R) -1-benzyl-3-chloro-1-methyl-but-3-enyl) -8-fluoro-quinoline-3-carboxamide, N- ((1S) -1-benzyl-3-chloro-1-methyl-but-3-enyl) -8-fluoro-quinoline-3-carboxamide, (Z) -3-methoxy-2- [ 2-methyl-5- [4- (trifluoromethyl) triazol-2-yl ] phenoxy ] prop-2-enoic acid methyl ester, (Z) -3-methoxy-2- [ 2-methyl-5- (4-propyltriazol-2-yl) phenoxy ] prop-2-enoic acid methyl ester, (Z) -2- [5- (3-isopropylpyrazol-1-yl) -2-methyl-phenoxy ] -3-methoxy-prop-2-enoic acid methyl ester, Methyl (Z) -3-methoxy-2- [ 2-methyl-5- (3-propylpyrazol-1-yl) phenoxy ] prop-2-enoate, methyl (Z) -3-methoxy-2- [ 2-methyl-5- [3- (trifluoromethyl) pyrazol-1-yl ] phenoxy ] prop-2-enoate, methyl (Z) -2- (5-cyclohexyl-2-methyl-phenoxy) -3-methoxy-prop-2-enoate, methyl (Z) -2- (5-cyclopentyl-2-methyl-phenoxy) -3-methoxy-prop-2-enoate (these compounds can be prepared by the methods described in WO 2020/193387), methyl (Z) -3-methoxy-prop-2-enoate, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -5-methyl-N-spiro [3.4] oct-3-yl-thiazole-4-carboxamide, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -N-hexyl-5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (2-methoxyacetyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (tetrahydropyran-4-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (oxetane-3-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (tetrahydrofuran-3-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ acetyl- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (2-methylpropanoyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, TAEGRO (i.e. bacillus amyloliquefaciens strain FZB 24), melaleuca alternifolia oil (melaleuca alternifolia extract (commercially available as Timorex Gold, which is a broad spectrum plant biological fungicide)), giant knotweed extract (commercially available as REGALIA), a plant extract based on a lycopodium clavatum extract (commercially available as BOTRISTOP), or aureobasidin a, wherein the weight ratio of component (a) to component (B) is from 10:1 to 1:10 (or even more preferably, 5:1 to 1:5).

In another still more preferred composition according to the invention, component (A) is compound number X.09, [5- (2, 4-difluorophenyl) isoxazol-3-yl ] - [7- (1, 5-dimethylpyrazol-4-yl) -6, 7-dihydro-4H-thiadiazolo [4,5-c ] pyridin-5-yl ] methanone (X.09), or a salt enantiomer, tautomer, or N-oxide thereof, and component (B) is a compound selected from the group consisting of fluxapyroxad hydroxylamine, benzovindiflupyr, bipyramid, fluxapyroxad, isopyrazamide, pyrithioflupyr-containing, fluxapyroxad, Trifloxystrobin, azoxystrobin, tetrazolidone picolide, picolinamide trifloxystrobin, azoxystrobin, tetrazolidone, picolide, picolinamide, trifloxystrobin, picolinamide, and pyrad hoc, or mixtures thereof Pyridinamide, fluazinam, fenpropidin, cyproconazole difenoconazole, metconazole, penconazole, propiconazole, tebuconazole, penconazole, prothioconazole, penoxsulam, triflumizole, triflumuron, iprovalicarb, triflumuron, metalaxyl-M, cyprodinil, pyrimethanil, mancozeb, copper compounds (different salts), sulfur, folpet, chlorothalonil, dithianon, propioquinoline, trifloxystrobin, Fludioxonil, benzofuranone, fluorothiazolyl ethanone, trifloxysulf, alamic acid type benzene-S-methyl, phosphorous acid, cyflufenamid, tricyclazole, N-methoxy-N- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] cyclopropanecarboxamide, N, 2-dimethoxy-N- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] propionamide, 1-methoxy-3-methyl-1- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] urea, 1, 3-dimethoxy-1- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] urea, N- [ (1R) -1-benzyl-3-chloro-1-methyl-but-3-enyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-3-chloro-1-methyl-but-3-enyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1R) -1-benzyl-3, 3-trifluoro-1-methyl-propyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-3, 3-trifluoro-1-methyl-propyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl ] -7, 8-difluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-1, 3-dimethyl-butyl ] -7, 8-difluoro-quinoline-3-carboxamide, 8-fluoro-N- [ (1R) -1- [ (3-fluorophenyl) methyl ] -1, 3-dimethyl-butyl ] quinoline-3-carboxamide, 8-fluoro-N- [ (1S) -1- [ (3-fluorophenyl) methyl ] -1, 3-dimethyl-butyl ] quinoline-3-carboxamide, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, N- ((1R) -1-benzyl-3-chloro-1-methyl-but-3-enyl) -8-fluoro-quinoline-3-carboxamide, N- ((1S) -1-benzyl-3-chloro-1-methyl-but-3-enyl) -8-fluoro-quinoline-3-carboxamide, (Z) -3-methoxy-2- [ 2-methyl-5- [4- (trifluoromethyl) triazol-2-yl ] phenoxy ] prop-2-enoic acid methyl ester, (Z) -3-methoxy-2- [ 2-methyl-5- (4-propyltriazol-2-yl) phenoxy ] prop-2-enoic acid methyl ester, (Z) -2- [5- (3-isopropylpyrazol-1-yl) -2-methyl-phenoxy ] -3-methoxy-prop-2-enoic acid methyl ester, Methyl (Z) -3-methoxy-2- [ 2-methyl-5- (3-propylpyrazol-1-yl) phenoxy ] prop-2-enoate, methyl (Z) -3-methoxy-2- [ 2-methyl-5- [3- (trifluoromethyl) pyrazol-1-yl ] phenoxy ] prop-2-enoate, methyl (Z) -2- (5-cyclohexyl-2-methyl-phenoxy) -3-methoxy-prop-2-enoate, methyl (Z) -2- (5-cyclopentyl-2-methyl-phenoxy) -3-methoxy-prop-2-enoate (these compounds can be prepared by the methods described in WO 2020/193387), methyl (Z) -3-methoxy-prop-2-enoate, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -5-methyl-N-spiro [3.4] oct-3-yl-thiazole-4-carboxamide, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -N-hexyl-5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (2-methoxyacetyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (tetrahydropyran-4-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (oxetane-3-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (tetrahydrofuran-3-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ acetyl- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (2-methylpropanoyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, TAEGRO (i.e. bacillus amyloliquefaciens strain FZB 24), melaleuca alternifolia oil (melaleuca alternifolia extract (commercially available as Timorex Gold, which is a broad spectrum plant biological fungicide)), giant knotweed extract (commercially available as REGALIA), a plant extract based on a lycopodium clavatum extract (commercially available as BOTRISTOP), or aureobasidin a, wherein the weight ratio of component (a) to component (B) is from 10:1 to 1:10 (or even more preferably, 5:1 to 1:5).

In another still more preferred composition according to the invention, component (a) is compound number x.10: [5- (2, 4-difluorophenyl) isoxazol-3-yl ] - [7- (1, 5-dimethylpyrazol-4-yl) -6, 7-dihydro-4H-thieno [3,2-c ] pyridin-5-yl ] methanone (X.10), or a salt enantiomer, tautomer, or N-oxide thereof, and component (B) is a compound selected from the group consisting of fluxapyroxad hydroxylamine, benzovindiflupyr, bixafen, fluxapyroxad, isopyrazam, penthiopyrad, epoxiconamine, boscalid, fluopicolide, thiaflufenamide, bixafen, iprovalicarb, indenopyrazolam, penconazole, triflumamid, pyraclostrobin, trifloxystrobin, azoxystrobin, tetrazolidone, picolide, picolinamide, fluazinam, fenpropidin, fenhexamid, cyproconazole, difenoconazole, trifloxystrobin, fenpropiconazole, fenpropion-methyl, and the like metconazole, penconazole, propiconazole, tebuconazole, penconazole, prothioconazole, penconazole, triflumizole, iprovalicarb, triflumuron, metalaxyl-M, cyprodinil, pyrimethanil, mancozeb, copper compounds (different salts), sulfur, folpet, chlorothalonil, dithianon, propioquinoline, fludioxonil, Benzofuranone, fluorothiazolyl ethanone, fluorooxazamate, alamic acid-benzene-S-methyl, phosphorous acid, cyflufenamid, tricyclazole, N-methoxy-N- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] cyclopropanecarboxamide, N, 2-dimethoxy-N- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] propionamide, 1-methoxy-3-methyl-1- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] urea, 1, 3-dimethoxy-1- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] urea, N- [ (1R) -1-benzyl-3-chloro-1-methyl-but-3-enyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-3-chloro-1-methyl-but-3-enyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1R) -1-benzyl-3, 3-trifluoro-1-methyl-propyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-3, 3-trifluoro-1-methyl-propyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl ] -7, 8-difluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-1, 3-dimethyl-butyl ] -7, 8-difluoro-quinoline-3-carboxamide, 8-fluoro-N- [ (1R) -1- [ (3-fluorophenyl) methyl ] -1, 3-dimethyl-butyl ] quinoline-3-carboxamide, 8-fluoro-N- [ (1S) -1- [ (3-fluorophenyl) methyl ] -1, 3-dimethyl-butyl ] quinoline-3-carboxamide, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, N- ((1R) -1-benzyl-3-chloro-1-methyl-but-3-enyl) -8-fluoro-quinoline-3-carboxamide, N- ((1S) -1-benzyl-3-chloro-1-methyl-but-3-enyl) -8-fluoro-quinoline-3-carboxamide, (Z) -3-methoxy-2- [ 2-methyl-5- [4- (trifluoromethyl) triazol-2-yl ] phenoxy ] prop-2-enoic acid methyl ester, (Z) -3-methoxy-2- [ 2-methyl-5- (4-propyltriazol-2-yl) phenoxy ] prop-2-enoic acid methyl ester, (Z) -2- [5- (3-isopropylpyrazol-1-yl) -2-methyl-phenoxy ] -3-methoxy-prop-2-enoic acid methyl ester, Methyl (Z) -3-methoxy-2- [ 2-methyl-5- (3-propylpyrazol-1-yl) phenoxy ] prop-2-enoate, methyl (Z) -3-methoxy-2- [ 2-methyl-5- [3- (trifluoromethyl) pyrazol-1-yl ] phenoxy ] prop-2-enoate, methyl (Z) -2- (5-cyclohexyl-2-methyl-phenoxy) -3-methoxy-prop-2-enoate, methyl (Z) -2- (5-cyclopentyl-2-methyl-phenoxy) -3-methoxy-prop-2-enoate (these compounds can be prepared by the methods described in WO 2020/193387), methyl (Z) -3-methoxy-prop-2-enoate, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -5-methyl-N-spiro [3.4] oct-3-yl-thiazole-4-carboxamide, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -N-hexyl-5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (2-methoxyacetyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (tetrahydropyran-4-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (oxetane-3-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (tetrahydrofuran-3-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ acetyl- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (2-methylpropanoyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, TAEGRO (i.e. bacillus amyloliquefaciens strain FZB 24), melaleuca alternifolia oil (melaleuca alternifolia extract (commercially available as Timorex Gold, which is a broad spectrum plant biological fungicide)), giant knotweed extract (commercially available as REGALIA), a plant extract based on a lycopodium clavatum extract (commercially available as BOTRISTOP), or aureobasidin a, wherein the weight ratio of component (a) to component (B) is from 10:1 to 1:10 (or even more preferably, 5:1 to 1:5).

In another still more preferred composition according to the invention, component (A) is compound number X.11 [5- (2, 4-difluorophenyl) isoxazol-3-yl ] - [ rac- (4S, 7S) -7- (1, 5-dimethylpyrazol-4-yl) -4-methyl-6, 7-dihydro-4H-thieno [3,2-c ] pyridin-5-yl ] methanone, or a salt enantiomer, tautomer, or N-oxide thereof, and component (B) is a compound selected from the group consisting of fluxapyroxal hydroxylamine, benzovindiflupyr, bixafen, fluxapyroxad, isopyrazam, penthiopyrad, Cyproconazole, boscalid, fluopyram, thiaflufenamide, bixafen, flufenamid, and flufenamid, and the like penflufen, indene penflufen, fluoxastrobin, trifluoracetam, and iprovalicarb, indene pencycuron penflufen, triflumizole, penflufen and the like cyproconazole, difenoconazole, metconazole, penconazole, propiconazole, tebuconazole, difenoconazole, prothioconazole, penconazole, trifloxystrobin, triflumizole, iprovalicarb, quinoline trifloxystrobin, metalaxyl-M, cyprodinil, pyrimethanil, mancozeb, copper compounds (different salts), sulfur, folpet, chlorothalonil, dithianon, Propoxyquinoline, fludioxonil, benzofuranone, fluorothiazolyl pyrithione, trifloxysulfate, alamic acid type benzene-S-methyl, phosphorous acid, cyflufenamid, tricyclazole, N-methoxy-N- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] cyclopropanecarboxamide, N, 2-dimethoxy-N- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] propionamide, 1-methoxy-3-methyl-1- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] urea, 1, 3-dimethoxy-1- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] urea, N- [ (1R) -1-benzyl-3-chloro-1-methyl-but-3-enyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-3-chloro-1-methyl-but-3-enyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1R) -1-benzyl-3, 3-trifluoro-1-methyl-propyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-3, 3-trifluoro-1-methyl-propyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl ] -7, 8-difluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-1, 3-dimethyl-butyl ] -7, 8-difluoro-quinoline-3-carboxamide, 8-fluoro-N- [ (1R) -1- [ (3-fluorophenyl) methyl ] -1, 3-dimethyl-butyl ] quinoline-3-carboxamide, 8-fluoro-N- [ (1S) -1- [ (3-fluorophenyl) methyl ] -1, 3-dimethyl-butyl ] quinoline-3-carboxamide, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, N- ((1R) -1-benzyl-3-chloro-1-methyl-but-3-enyl) -8-fluoro-quinoline-3-carboxamide, N- ((1S) -1-benzyl-3-chloro-1-methyl-but-3-enyl) -8-fluoro-quinoline-3-carboxamide, (Z) -3-methoxy-2- [ 2-methyl-5- [4- (trifluoromethyl) triazol-2-yl ] phenoxy ] prop-2-enoic acid methyl ester, (Z) -3-methoxy-2- [ 2-methyl-5- (4-propyltriazol-2-yl) phenoxy ] prop-2-enoic acid methyl ester, (Z) -2- [5- (3-isopropylpyrazol-1-yl) -2-methyl-phenoxy ] -3-methoxy-prop-2-enoic acid methyl ester, Methyl (Z) -3-methoxy-2- [ 2-methyl-5- (3-propylpyrazol-1-yl) phenoxy ] prop-2-enoate, methyl (Z) -3-methoxy-2- [ 2-methyl-5- [3- (trifluoromethyl) pyrazol-1-yl ] phenoxy ] prop-2-enoate, methyl (Z) -2- (5-cyclohexyl-2-methyl-phenoxy) -3-methoxy-prop-2-enoate, methyl (Z) -2- (5-cyclopentyl-2-methyl-phenoxy) -3-methoxy-prop-2-enoate (these compounds can be prepared by the methods described in WO 2020/193387), methyl (Z) -3-methoxy-prop-2-enoate, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -5-methyl-N-spiro [3.4] oct-3-yl-thiazole-4-carboxamide, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -N-hexyl-5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (2-methoxyacetyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (tetrahydropyran-4-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (oxetane-3-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (tetrahydrofuran-3-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ acetyl- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (2-methylpropanoyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, TAEGRO (i.e. bacillus amyloliquefaciens strain FZB 24), melaleuca alternifolia oil (melaleuca alternifolia extract (commercially available as Timorex Gold, which is a broad spectrum plant biological fungicide)), giant knotweed extract (commercially available as REGALIA), a plant extract based on a lycopodium clavatum extract (commercially available as BOTRISTOP), or aureobasidin a, wherein the weight ratio of component (a) to component (B) is from 10:1 to 1:10 (or even more preferably, 5:1 to 1:5).

In an even more preferred composition according to the invention component (A) is compound number X.01, [5- (2, 4-difluorophenyl) -1,3, 4-thiadiazol-2-yl ] - [ (4R, 7S) -4, 7-dimethyl-4- (1-methylpyrazol-4-yl) -5, 7-dihydrothieno [2,3-c ] pyridin-6-yl ] methanone (X.01), or a salt enantiomer, tautomer, or N-oxide thereof, and component (B) is a compound selected from the group consisting of fluxazoyl hydroxylamine, benzovinfluxazole, azoxystrobin, picolinide, difenoconazole, prothioconazole, triflumizole, cyprodinil, fludioxonil, an arabino-benzene-S-methyl, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-3-dimethyl-3-quinoline-carboxamide, N- [ (1S) -1, 3-difluoro-butyl-3-2-fluoro-butan-3-carboxamide, N-fluoro- [ 4-methyl ] -4-cyano-4-2-cyano ] -3-tetramethyl-2-carboxamide, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (tetrahydropyran-4-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ acetyl- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, TAEGRO @ (i.e. bacillus amyloliquefaciens strain FZB 24), melaleuca alternifolia oil (tea plant melaleuca extract (commercially available as Timorex Gold, which is a broad-spectrum plant biological fungicide)), giant knotweed extract (commercially available as REGALIA), a plant extract based on a lycopodium extract (commercially available as BOTRISTOP), or aurin a, wherein the weight ratio of component (a) to component (B) is from 1 to 5:10 or even more preferably from 1:1 to 5:1.

In another even more preferred composition according to the invention component (A) is compound number X.02- [5- (2, 4-difluorophenyl) isoxazol-3-yl ] - [ rac- (4S, 7R) -4, 7-dimethyl-4- (1-methylpyrazol-4-yl) -5, 7-dihydrothieno [2,3-c ] pyridin-6-yl ] methanone (X.02), or a salt enantiomer, tautomer, or N-oxide thereof, and component (B) is a compound selected from the group consisting of fluxapyroxal, benzovindiflupyr, azoxystrobin, picolinide, difenoconazole, prothioconazole, triflumizole, fludioxonil, arabino-benzene-S-methyl, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-3-dimethyl-3-butyl ] -3-carboxamide, N- [ (1S) -1-2-difluoro-3-methyl-4-2-fluoro-2- [ 3-fluoro-2-fluoro-butanamide, 3-fluoro-2-fluoro-methyl-4-cyano ] -N-3-fluoro-carboxamide, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (tetrahydropyran-4-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ acetyl- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, TAEGRO @ (i.e. bacillus amyloliquefaciens strain FZB 24), melaleuca alternifolia oil (tea plant melaleuca extract (commercially available as Timorex Gold, which is a broad-spectrum plant biological fungicide)), giant knotweed extract (commercially available as REGALIA), a plant extract based on a lycopodium extract (commercially available as BOTRISTOP), or aurin a, wherein the weight ratio of component (a) to component (B) is from 1 to 5:10 or even more preferably from 1:1 to 5:1.

In another even more preferred composition according to the invention component (A) is compound number X.03- [5- (2, 4-difluorophenyl) isoxazol-3-yl ] - [ rac- (4R, 7S) -7-methyl-4- (1-methylpyrazol-4-yl) -5, 7-dihydro-4H-thieno [2,3-c ] pyridin-6-yl ] methanone (X.03), or a salt enantiomer, tautomer, or N-oxide thereof, and component (B) is a compound selected from the group consisting of fluxazoyl hydroxylamine, benzovinfluxazole, azoxystrobin, picolinide, difenoconazole, prothioconazole, triflumizole, cyprodinil, fludioxonil, an arabino-benzene-S-methyl, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-3-dimethyl-3-quinoline-carboxamide, N- [2, 3-difluoro-3-methylbenzyl ] -3-carboxamide, N- [ 2-fluoro-3-methyl ] -4-2-fluoro-2-methyl-4-N-2-fluoro-butan-3-yl ] -N-methyl-3-yl-carboxamide, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (tetrahydropyran-4-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ acetyl- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, TAEGRO @ (i.e. bacillus amyloliquefaciens strain FZB 24), melaleuca alternifolia oil (tea plant melaleuca extract (commercially available as Timorex Gold, which is a broad-spectrum plant biological fungicide)), giant knotweed extract (commercially available as REGALIA), a plant extract based on a lycopodium extract (commercially available as BOTRISTOP), or aurin a, wherein the weight ratio of component (a) to component (B) is from 1 to 5:10 or even more preferably from 1:1 to 5:1.

In another even more preferred composition according to the invention component (A) is compound number X.04, [5- (2, 4-difluorophenyl) -1,3, 4-thiadiazol-2-yl ] - [ rac- (4R, 7S) -7-methyl-4- (1-methylpyrazol-4-yl) -5, 7-dihydro-4H-thieno [2,3-c ] pyridin-6-yl ] methanone (X.04), or a salt enantiomer, tautomer, or N-oxide thereof, and component (B) is a compound selected from the group consisting of fluxazoylhydroxylamine, benzovinfluxazole, azoxystrobin, picolinide, difenoconazole, prothioconazole, penfluquin-ethyl, azoxystrobin, fludioxonil, arabino-benzol-methyl, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinolin-3-carboxamide, N- [ (1-S) -1-benzyl-3-fluoro-3-carboxamide, N- [ (1-dimethyl-butyl ] -8-fluoro-quinolin-3-yl ] -2-yl-fluxazin-3-yl ] -2-yl-fluxazole, 3-yl-fluxazoxazole 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (tetrahydropyran-4-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ acetyl- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, TAEGRO @ (i.e. bacillus amyloliquefaciens strain FZB 24), melaleuca alternifolia oil (tea plant melaleuca extract (commercially available as Timorex Gold, which is a broad-spectrum plant biological fungicide)), giant knotweed extract (commercially available as REGALIA), a plant extract based on a lycopodium extract (commercially available as BOTRISTOP), or aurin a, wherein the weight ratio of component (a) to component (B) is from 1 to 5:10 or even more preferably from 1:1 to 5:1.

In another even more preferred composition according to the invention component (A) is compound number X.05, [5- (2, 4-difluorophenyl) -1,3, 4-thiadiazol-2-yl ] - [ 4-methyl-4- (1-methylpyrazol-4-yl) -5, 7-dihydrothieno [2,3-c ] pyridin-6-yl ] methanone (X.05), or a salt enantiomer, tautomer, or N-oxide thereof, and component (B) is a compound selected from the group consisting of fluxazoxamide, benzovindiflupyr, azoxystrobin, picolinide, difenoconazole, prothioconazole, haloxypyr, cyprodinil, fludioxonil, an arabino-benzene-S-methyl, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-1, 3-dimethyl-8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-dimethyl-3-8-fluoro-quinoline-3-carboxamide, N- [ 2-fluoro-4-cyano ] -2-fluoro-4-spiroxamide, N-fluoro-3-carboxamide, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (tetrahydropyran-4-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ acetyl- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, TAEGRO @ (i.e. bacillus amyloliquefaciens strain FZB 24), melaleuca alternifolia oil (tea plant melaleuca extract (commercially available as Timorex Gold, which is a broad-spectrum plant biological fungicide)), giant knotweed extract (commercially available as REGALIA), a plant extract based on a lycopodium extract (commercially available as BOTRISTOP), or aurin a, wherein the weight ratio of component (a) to component (B) is from 1 to 5:10 or even more preferably from 1:1 to 5:1.

In another even more preferred composition according to the invention component (A) is compound number X.06- [5- (2, 4-difluorophenyl) isoxazol-3-yl ] - [ 4-methyl-4- (1-methylpyrazol-4-yl) -5, 7-dihydrothieno [2,3-c ] pyridin-6-yl ] methanone (X.06), or a salt enantiomer, tautomer, or N-oxide thereof, and component (B) is a compound selected from the group consisting of fluxazoxamide, benzovindiflupyr, azoxystrobin, picolinamide, difenoconazole, prothioconazole, penconazole, cyprodinil, fludioxonil, the arabino-benzene-S-methyl, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-3-quinoline-3-carboxamide, N- [ 2- (4-fluoro-spiroxamide, N- [ (1S) -1-dimethyl-butyl ] -8-fluoro-3-carboxamide, N- [ 4-fluoro-cyano ] -4-methyl-4-N-4-carbamide, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (tetrahydropyran-4-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ acetyl- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, TAEGRO @ (i.e. bacillus amyloliquefaciens strain FZB 24), melaleuca alternifolia oil (tea plant melaleuca extract (commercially available as Timorex Gold, which is a broad-spectrum plant biological fungicide)), giant knotweed extract (commercially available as REGALIA), a plant extract based on a lycopodium extract (commercially available as BOTRISTOP), or aurin a, wherein the weight ratio of component (a) to component (B) is from 1 to 5:10 or even more preferably from 1:1 to 5:1.

In another even more preferred composition according to the invention component (A) is compound number X.07, [5- (2, 4-difluorophenyl) isoxazol-3-yl ] - [ 7-methyl-7- (1-methylpyrazol-4-yl) -4, 6-dihydrothieno [3,2-c ] pyridin-5-yl ] methanone (X.07), or a salt enantiomer, tautomer, or N-oxide thereof, and component (B) is a compound selected from the group consisting of fluxazoxamide, benzovindiflupyr, azoxystrobin, picolinamide, difenoconazole, prothioconazole, penflufen, cyprodinil, fludioxonil, the arabino-benzene-S-methyl, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-3-quinoline-3-carboxamide, N- [ 2- (4-fluoro-spiroxamide, N- [ (1S) -1-dimethyl-butyl ] -8-fluoro-3-carboxamide, N- [ 2-fluoro-3-spiroxamide ] -2- [ 4-methyl-4-cyano ] -4-cyano-N-4-carbamide, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (tetrahydropyran-4-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ acetyl- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, TAEGRO @ (i.e. bacillus amyloliquefaciens strain FZB 24), melaleuca alternifolia oil (tea plant melaleuca extract (commercially available as Timorex Gold, which is a broad-spectrum plant biological fungicide)), giant knotweed extract (commercially available as REGALIA), a plant extract based on a lycopodium extract (commercially available as BOTRISTOP), or aurin a, wherein the weight ratio of component (a) to component (B) is from 1 to 5:10 or even more preferably from 1:1 to 5:1.

In another even more preferred composition according to the invention component (A) is compound number X.08, [5- (2, 4-difluorophenyl) isoxazol-3-yl ] - [4- (1-methylpyrazol-4-yl) -5, 7-dihydro-4H-isothiazolo [5,4-c ] pyridin-6-yl ] methanone (X.08), or a salt enantiomer, tautomer, or N-oxide thereof, and component (B) is a compound selected from the group consisting of fluxazoxamide, benzovindiflupyr, azoxystrobin, picolinamide, difenoconazole, prothioconazole, difenoconazole, cyprodinil, fludioxonil, alamic acid-type benzene-S-methyl, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-3-fluoro-quinoline-3-carboxamide, N- [ 2- (4-cyano-3-spiro-2-4-oxamide ] amino-2, 4-fluoro-3-carboxamide, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (tetrahydropyran-4-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ acetyl- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, TAEGRO @ (i.e. bacillus amyloliquefaciens strain FZB 24), melaleuca alternifolia oil (tea plant melaleuca extract (commercially available as Timorex Gold, which is a broad-spectrum plant biological fungicide)), giant knotweed extract (commercially available as REGALIA), a plant extract based on a lycopodium extract (commercially available as BOTRISTOP), or aurin a, wherein the weight ratio of component (a) to component (B) is from 1 to 5:10 or even more preferably from 1:1 to 5:1.

In another even more preferred composition according to the invention component (A) is compound number X.09- [5- (2, 4-difluorophenyl) isoxazol-3-yl ] - [7- (1, 5-dimethylpyrazol-4-yl) -6, 7-dihydro-4H-thiadiazolo [4,5-c ] pyridin-5-yl ] methanone (X.09), or a salt enantiomer, tautomer, or N-oxide thereof, and component (B) is a compound selected from the group consisting of fluxazoxamide, benzovindiflupyr, azoxystrobin, picolinide, difenoconazole, prothioconazole, halofop-butyl, cyprodinil, fludioxonil, arabino-benzene-S-methyl, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-dimethyl-8-fluoro-3-fluoro-quinoline-3-carboxamide, N- [ 2-fluoro-4-cyano ] -2- [2, 3-fluoro-2-tetramethyl-3-carboxamide, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (tetrahydropyran-4-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ acetyl- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, TAEGRO @ (i.e. bacillus amyloliquefaciens strain FZB 24), melaleuca alternifolia oil (tea plant melaleuca extract (commercially available as Timorex Gold, which is a broad-spectrum plant biological fungicide)), giant knotweed extract (commercially available as REGALIA), a plant extract based on a lycopodium extract (commercially available as BOTRISTOP), or aurin a, wherein the weight ratio of component (a) to component (B) is from 1 to 5:10 or even more preferably from 1:1 to 5:1.

In another even more preferred composition according to the invention component (A) is compound number X.10, [5- (2, 4-difluorophenyl) isoxazol-3-yl ] - [7- (1, 5-dimethylpyrazol-4-yl) -6, 7-dihydro-4H-thieno [3,2-c ] pyridin-5-yl ] methanone (X.10), or a salt enantiomer, tautomer, or N-oxide thereof, and component (B) is a compound selected from the group consisting of fluxazoxamide, benzovindiflupyr, azoxystrobin, picolinide, difenoconazole, prothioconazole, halofop-butyl, cyprodinil, arabino-benzene-S-methyl, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-1, 3-dimethyl-8-fluoro-quinoline-3-fluoro-3-carboxamide, N- [ 4-cyano ] -3-spiro-4-carboxamide, N- [ 4-fluoro-3-carboxamide, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (tetrahydropyran-4-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ acetyl- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, TAEGRO @ (i.e. bacillus amyloliquefaciens strain FZB 24), melaleuca alternifolia oil (tea plant melaleuca extract (commercially available as Timorex Gold, which is a broad-spectrum plant biological fungicide)), giant knotweed extract (commercially available as REGALIA), a plant extract based on a lycopodium extract (commercially available as BOTRISTOP), or aurin a, wherein the weight ratio of component (a) to component (B) is from 1 to 5:10 or even more preferably from 1:1 to 5:1.

In another even more preferred composition according to the invention component (A) is compound number X.11- [5- (2, 4-difluorophenyl) isoxazol-3-yl ] - [ rac- (4S, 7S) -7- (1, 5-dimethylpyrazole-4-yl) -4-methyl-6, 7-dihydro-4H-thieno [3,2-c ] pyridin-5-yl ] methanone, or a salt enantiomer, tautomer, or N-oxide thereof, and component (B) is a compound selected from the group consisting of fluxapyroxal, benzovindiflupyr, azoxystrobin, picolinide, difenoconazole, prothioconazole, triflumizole, fludioxonil, arabino-benzene-S-methyl, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-3-dimethyl-3-butyl ] -3-carboxamide, N- [ (1S) -1-2-difluoro-3-methyl-3-2-fluoro-2- [ 3-fluoro-2-fluoro-butanamide, 3-fluoro-2-fluoro-N-3-yl ] -N-fluoro-butanamide 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (tetrahydropyran-4-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ acetyl- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, TAEGRO @ (i.e. bacillus amyloliquefaciens strain FZB 24), melaleuca alternifolia oil (tea plant melaleuca extract (commercially available as Timorex Gold, which is a broad-spectrum plant biological fungicide)), giant knotweed extract (commercially available as REGALIA), a plant extract based on a lycopodium extract (commercially available as BOTRISTOP), or aurin a, wherein the weight ratio of component (a) to component (B) is from 1 to 5:10 or even more preferably from 1:1 to 5:1.

In an even more preferred composition according to the invention, component (A) is compound number X.01, [5- (2, 4-difluorophenyl) -1,3, 4-thiadiazol-2-yl ] - [ (4R, 7S) -4, 7-dimethyl-4- (1-methylpyrazol-4-yl) -5, 7-dihydrothieno [2,3-c ] pyridin-6-yl ] methanone (X.01), or a salt enantiomer, tautomer, or N-oxide thereof, and component (B) is a compound selected from the group consisting of fluxapyroxad hydroxylamine, benzovindiflupyr, azoxystrobin, picolide, difenoconazole, prothioconazole, triflumizole, fludioxonil, or an ara-type benzene-S-methyl, wherein the weight ratio of component (A) to component (B) is from 10:1 to 10 (or even more preferably, from 1:5:1 to 5).

In an even more preferred composition according to the invention, component (A) is compound number X.02- [5- (2, 4-difluorophenyl) isoxazol-3-yl ] - [ rac- (4S, 7R) -4, 7-dimethyl-4- (1-methylpyrazol-4-yl) -5, 7-dihydrothieno [2,3-c ] pyridin-6-yl ] methanone (X.02), or a salt enantiomer, tautomer, or N-oxide thereof, and component (B) is a compound selected from the group consisting of fluxapyroxal hydroxylamine, benzovindiflupyr, azoxystrobin, picolide, difenoconazole, prothioconazole, haloxypyr-l, cyprodinil, fludioxonil, or an arabino-benzene-S-methyl, wherein the weight ratio of component (A) to component (B) is from 10:1 to 1:10 (or even more preferably 5:1 to 1:5).

In an even more preferred composition according to the invention, component (A) is compound number X.03 [5- (2, 4-difluorophenyl) isoxazol-3-yl ] - [ rac- (4R, 7S) -7-methyl-4- (1-methylpyrazol-4-yl) -5, 7-dihydro-4H-thieno [2,3-c ] pyridin-6-yl ] methanone (X.03), or a salt enantiomer, tautomer, or N-oxide thereof, and component (B) is a compound selected from the group consisting of fluxapyroxal, benzovindiflupyr, azoxystrobin, picolide, difenoconazole, prothioconazole, triflumizole, fludioxonil, or an araboxylic acid benzene-S-methyl, wherein the weight ratio of component (A) to component (B) is from 10:1 to 1:10 (or even more preferably, 5:1 to 5).

In an even more preferred composition according to the invention, component (A) is compound number X.04- [5- (2, 4-difluorophenyl) -1,3, 4-thiadiazol-2-yl ] - [ rac- (4R, 7S) -7-methyl-4- (1-methylpyrazol-4-yl) -5, 7-dihydro-4H-thieno [2,3-c ] pyridin-6-yl ] methanone (X.04), or a salt enantiomer, tautomer, or N-oxide thereof, and component (B) is a compound selected from the group consisting of fluxazoacyl hydroxylamine, benzovindiflumella, azoxystrobin, picolide, difenoconazole, prothioconazole, penflufen, cyprodinil, fludioxonil, or an arabino-benzene-S-methyl, wherein the weight ratio of component (A) to component (B) is from 10:1 to 10 (or even more preferably from 1:5:1 to 5).

In an even more preferred composition according to the invention, component (A) is compound number X.05, [5- (2, 4-difluorophenyl) -1,3, 4-thiadiazol-2-yl ] - [ 4-methyl-4- (1-methylpyrazol-4-yl) -5, 7-dihydrothieno [2,3-c ] pyridin-6-yl ] methanone (X.05), or a salt enantiomer, tautomer, or N-oxide thereof, and component (B) is a compound selected from the group consisting of fluxazoyl hydroxylamine, benzovindiflupyr, azoxystrobin, picolinide, difenoconazole, prothioconazole, trifloxystrobin, cyprodinil, fludioxonil, or an ara-benzene-S-methyl, wherein the weight ratio of component (A) to component (B) is from 10:1 to 10 (or even more preferably, 5:1 to 1:5).

In an even more preferred composition according to the invention, component (A) is compound number X.06 [5- (2, 4-difluorophenyl) isoxazol-3-yl ] - [ 4-methyl-4- (1-methylpyrazol-4-yl) -5, 7-dihydrothieno [2,3-c ] pyridin-6-yl ] methanone (X.06), or a salt enantiomer, tautomer, or N-oxide thereof, and component (B) is a compound selected from the group consisting of fluxapyroxad hydroxylamine, benzovindiflupyr, azoxystrobin, picolinamide, difenoconazole, prothioconazole, triflumizole, cyprodinil, fludioxonil, or an ara-benzene-S-methyl, wherein the weight ratio of component (A) to component (B) is from 10:1 to 1:10 (or even more preferably 5:1 to 1:5).

In an even more preferred composition according to the invention, component (A) is compound number X.07, [5- (2, 4-difluorophenyl) isoxazol-3-yl ] - [ 7-methyl-7- (1-methylpyrazol-4-yl) -4, 6-dihydrothieno [3,2-c ] pyridin-5-yl ] methanone (X.07), or a salt enantiomer, tautomer, or N-oxide thereof, and component (B) is a compound selected from the group consisting of fluxapyroxad hydroxylamine, benzovindiflupyr, azoxystrobin, picolinamide, difenoconazole, prothioconazole, triflumizole, cyprodinil, fludioxonil, or an ara-benzene-S-methyl, wherein the weight ratio of component (A) to component (B) is from 10:1 to 1:10 (or even more preferably 5:1 to 1:5).

In an even more preferred composition according to the invention, component (A) is compound number X.08, [5- (2, 4-difluorophenyl) isoxazol-3-yl ] - [4- (1-methylpyrazol-4-yl) -5, 7-dihydro-4H-isothiazolo [5,4-c ] pyridin-6-yl ] methanone (X.08), or a salt enantiomer, tautomer, or N-oxide thereof, and component (B) is a compound selected from the group consisting of fluxapyroxad, benzovindiflupyr, azoxystrobin, picolinamide, difenoconazole, prothioconazole, triflumizole, cyprodinil, fludioxonil, or an ara-type benzene-S-methyl, wherein the weight ratio of component (A) to component (B) is from 10:1 to 1:10 (or even more preferably, 5:1 to 1:5).

In an even more preferred composition according to the invention, component (A) is compound number X.09, [5- (2, 4-difluorophenyl) isoxazol-3-yl ] - [7- (1, 5-dimethylpyrazol-4-yl) -6, 7-dihydro-4H-thiadiazolo [4,5-c ] pyridin-5-yl ] methanone (X.09), or a salt enantiomer, tautomer, or N-oxide thereof, and component (B) is a compound selected from the group consisting of fluxapyroxad hydroxylamine, benzovindiflupyr, azoxystrobin, picolinamide, difenoconazole, prothioconazole, triflumizole, fludioxonil, or an arabinoxylated benzene-S-methyl, wherein the weight ratio of component (A) to component (B) is from 10:1 to 10 (or even more preferably, 5:1 to 1:5).

In an even more preferred composition according to the invention, component (A) is compound number X.10, [5- (2, 4-difluorophenyl) isoxazol-3-yl ] - [7- (1, 5-dimethylpyrazol-4-yl) -6, 7-dihydro-4H-thieno [3,2-c ] pyridin-5-yl ] methanone (X.10), or a salt enantiomer, tautomer, or N-oxide thereof, and component (B) is a compound selected from the group consisting of fluxapyroxad, benzovindiflupyr, azoxystrobin, picolinamide, difenoconazole, prothioconazole, penconazole, cyprodinil, fludioxonil, or an araboxed benzene-S-methyl, wherein the weight ratio of component (A) to component (B) is from 10:1 to 1:10 (or even more preferably 5:1 to 1:5).

In an even more preferred composition according to the invention, component (A) is compound number X.11 [5- (2, 4-difluorophenyl) isoxazol-3-yl ] - [ rac- (4S, 7S) -7- (1, 5-dimethylpyrazol-4-yl) -4-methyl-6, 7-dihydro-4H-thieno [3,2-c ] pyridin-5-yl ] methanone, or a salt enantiomer, tautomer, or N-oxide thereof, and component (B) is a compound selected from the group consisting of fluxapyroxal hydroxylamine, benzovindiflupyr, azoxystrobin, picolide, difenoconazole, prothioconazole, haloxypyr-l, cyprodinil, fludioxonil, or an arabino-benzene-S-methyl, wherein the weight ratio of component (A) to component (B) is from 10:1 to 1:10 (or even more preferably 5:1 to 1:5).

In any of these compositions according to the invention, the composition may comprise a further active ingredient component (C), which is different from component (B) and is selected from the group consisting of: fluxapyroxad, benzovindiflupyr, bixafen, fluxapyroxad, isopyrazam, penflufen, pen penthiopyrad, cyproconazole, boscalid, fluopyram, thiaflufenamide, bixafen, penflufen penthiopyrad, cyproconazole, boscalid fluopyram, thiaflufenamide, bixafen, fluoxastrobin and fluoxastrobin, Trifloxystrobin, azoxystrobin, tetrazolidone, amisulbrom, cyazofamid, picolide Pyridinamide, pyridamide, flumetsulam, fluazinam, triphenyltin hydroxide Pyridinamide, picolinamide, flumetsulam, and zoxamide fluazinam, triphenyltin hydroxide epoxiconazole, flutriafol, hexaconazole, ipconazole, metconazole, myclobutanil penconazole, propiconazole, tebuconazole, fluoroether azole, triticonazole, prothioconazole penconazole, propiconazole, tebuconazole Fluor-ethoxazole, triticonazole, prothioconazole, and the like, Copper fungicides, sulfur, zinc thiazole, captan, folpet, chlorothalonil, dithianon, quinoxyfen, propioquinoline, fludioxonil, iprodione, procymidone, thiabendazole, zoxamide, metrafenone, fluopicolide, propamocarb, fluzopyr-diethyl ketone, trifloxysulf, alac acid type benzene-S-methyl, isothiabendamine, phosphorous acid, cyflufenamid, iso Ding Yiyang quinoline, tetrazolium picoline, tricyclazole, N-methoxy-N- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] cyclopropane-carboxamide, N, 2-dimethoxy-N- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] propionamide, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, methyl (Z) -2- (5-cyclohexyl-2-methyl-phenoxy) -3-methoxy-prop-2-enoate (which can be prepared by the method described in WO 2020/193387), 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -5-methyl-N-spiro [3.4] oct-3-yl-thiazole-4-carboxamide, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (2-methoxyacetyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (tetrahydropyran-4-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (oxetane-3-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (tetrahydrofuran-3-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ acetyl- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (2-methylpropionacyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, TAEGRO (i.e., bacillus amyloliquefaciens strain FZB 24), melaleuca alternifolia oil (melaleuca alternifolia extract (commercially available as Timorex Gold, which is a broad-spectrum plant biofungicide)), polygonum cuspidatum extract (commercially available as REGALIA), a plant extract, Plant extracts based on a lycopodium clavatum extract (commercially available as BOTRISTOP), or aureobasidin a.

Preferably, component (C), which is different from component (B), is a compound selected from the group consisting of: fluxapyroxad, benzovindiflupyr, bixafen, fluxapyroxad, isopyrazam, penthiopyrad, cyproconazole, fluxapyroxad, fluxad, penconazole, penciclovir, penciclov boscalid, fluopyram, thiaflufenamid, bixafen, ipflupyrad, indene picolide, fludanazol boscalid, fluopyram, thiaflufenamide, bixafen penflufen, indene penflufen, penflufen and the like, Fluor-ethoxazole, prothioconazole, haloxyfop-methyl, trifluoracer-oxazole, iprovalicarb, trifluoraceline, metalaxyl-M, cyprodinil, pyrimethanil, mancozeb, copper compounds (different salts), sulfur, folpet, chlorothalonil, dithianon, propioquinoline, fludioxonil, metrafenone, oxazodone, trifloxysulphate, alamic benzene-S-methyl, phosphorous acid, cyflufenamid, tricyclazole, N-methoxy-N- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] -cyclopropanecarboxamide, N, 2-dimethoxy-N- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] -propionamide, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, N- ((1R) -1-benzyl-3-chloro-1-methyl-but-3-enyl) -8-fluoro-quinoline-3-carboxamide, N- ((1S) -1-benzyl-3-chloro-1-methyl-but-3-enyl) -8-fluoro-quinoline-3-carboxamide, (Z) -2- (5-cyclohexyl-2-methyl-phenoxy) -3-methoxy-prop-2-enoic acid methyl ester (this compound can be prepared by the method described in WO 2020/193387), 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -5-methyl-N-spiro [3.4] oct-3-yl-thiazole-4-carboxamide, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (2-methoxyacetyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (tetrahydropyran-4-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (oxetane-3-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (tetrahydrofuran-3-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ acetyl- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (2-methylpropanoyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, TAEGRO (i.e., bacillus amyloliquefaciens strain FZB 24), melaleuca alternifolia oil (melaleuca alternifolia extract of the tea plant (commercially available as Timorex Gold, which is a broad-spectrum plant biofungstate)), polygonum cuspidatum extract (commercially available as REGALIA), a plant extract based on a lycopodium clavatum extract (commercially available as BOTRISTOP), or aureobasidin a.

Even more preferably, component (C), which is different from component (B), is a compound selected from the group consisting of fluxapyroxad hydroxylamine, benzovindiflupyr, trifloxystrobin, pyraclostrobin, azoxystrobin, tetrazolidone, picolinamide, fluazinam, fenpropidin, difenoconazole, metconazole, propiconazole, prothioconazole, penconazole, trifloxystrobin, fluxazole, cyprodinil, fludioxonil, N-methoxy-N- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] cyclopropanecarboxamide, N, 2-dimethoxy-N- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] propanamide, (Z) -2- (5-cyclohexyl-2-methyl-phenoxy) -3-methoxy-prop-2-enoic acid methyl ester, TAEGRO (i.e.e., bacillus dyssporefolium), leaf strain Fzem, or a herb extract of the plant (Qian) is commercially available as a commercial extract of the herb or as a commercial extract of the herb of the plant Cyperzia-Umbellifera herb 35 (35).

Even more preferably, component (C), which is different from component (B), is a compound selected from the group consisting of fluxapyroxad hydroxylamine, benzovindiflupyr, trifloxystrobin, pyraclostrobin, azoxystrobin, tetrazolidone, picolinamide, fluazinam, fenpropidin, difenoconazole, metconazole, propiconazole, prothioconazole, penconazole, trifloxystrobin, cyprodinil, fludioxonil, N-methoxy-N- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] cyclopropanecarboxamide, N, 2-dimethoxy-N- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] propionamide, or (Z) -2- (5-cyclohexyl-2-methyl-phenoxy) -3-methoxy-prop-2-enoic acid methyl ester.

In another embodiment of the present invention, there is provided a fungicidal composition comprising as active ingredients a mixture of component (A) and component (B) and component (C), wherein component (A) is a compound having formula (I) selected from the group consisting of compounds (X.01), (X.02), (X.03), (X.04), (X.05), (X.06), (X.07), (X.08), (X.09), (X.10), or (X.11), listed in Table X according to the present invention, and wherein component (C) and component (B) are compounds selected from the group consisting of fluxapyroxad hydroxylamine, Benzovindiflupyr, bixafen, fluxapyroxad, isopyrazam, penflufen, penflu penflufen, penthiopyrad, cyproconazole, boscalid, fluopyram, flupyraclostrobin, fluxapyroxad, penflufen, picolide, boscalid penflufen, penthiopyrad, cyproconazole, penflufen boscalid, fluopyram imidazolone, tolfenpyrad, picoxystrobin, pyraclostrobin, famoxadone kresoxim-methyl, trifloxystrobin, azoxystrobin, tetrazolidone, amisulbrom, and other drugs kresoxim-methyl, trifloxystrobin, azoxystrobin tetrazolidone, indazole sulfenamid, metconazole, myclobutanil, penconazole propiconazole, tebuconazole, fluoroether azole metconazole, myclobutanil, penconazole, propiconazole, tebuconazole, epoxiconazole, difenoconazole sterilizing azole, prothioconazole, fluopicolide, penflufen-penconazole, triflumizole, penconazole, penflufen-sodium, iprovalicarb, triflumuron, metalaxyl-M, cyprodinil, pyrimethanil, kasugamycin, mancozeb, copper fungicide, sulfur, zinc thiazole, captan, folpet, chlorothalonil, dithianon, quinoxyfen, propioquinoline, fludioxonil, iprodione, procymidone, thiabendazole, zoxamide, metrafenone, fluopicolide, Propamocarb, fluorothiazolyl ethanone, fluoxastrobin, alamic acid type benzene-S-methyl, isothiabendazole, phosphorous acid, cyflufenamid, iso Ding Yiyang quinoline, tetrazolium picolinate, tricyclazole, N-methoxy-N- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] cyclopropane-carboxamide, N, 2-dimethoxy-N- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] propionamide, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, N- [ (1S) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, (Z) -2- (5-cyclohexyl-2-methyl-phenoxy) -3-methoxy-prop-2-enoic acid methyl ester (this compound can be prepared by the method described in WO 2020/193387), 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -5-methyl-N-spiro [3.4] oct-3-yl-thiazole-4-carboxamide, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (2-methoxyacetyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (tetrahydropyran-4-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (oxetane-3-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (tetrahydrofuran-3-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ acetyl- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (2-methylpropanoyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, TAEGRO (i.e., bacillus amyloliquefaciens strain FZB 24), melaleuca alternifolia oil (melaleuca alternifolia extract (commercially available as Timorex Gold, which is a broad spectrum plant biological fungicide)), giant knotweed extract (commercially available as REGALIA), a plant extract based on a lycopodium clavatum extract (commercially available as BOTRISTOP), or aureobasidin a, and wherein components (B) and (C) are not the same compound.

Preferably, a fungicidal composition is provided, comprising as active ingredients a mixture of component (A) and component (B) and component (C), wherein component (A) is a compound of formula (I) selected from (X.01), (X.02), (X.03), (X.04), (X.05), (X.06), (X.07), (X.08), (X.09), (X.10), or (X.11), listed in Table X according to the present invention, and wherein component (C) and component (B) are compounds selected from the group consisting of fluxapyroxad hydroxylamine, Benzovindiflupyr, bixafen, fluxapyroxad, isopyrazam, penflufen, penflu penthiopyrad, cyproconazole, boscalid, fluopyram, thiaflufenamide, and the like penthiopyrad, cyproconazole, boscalid fluopyram, thiaflufenamide picolide, difluoropicolide, picolinamide, fluazinam, fenpropidin cyproconazole, difenoconazole, metconazole, penconazole, cyproconazole, difenoconazole, metconazole, difenoconazole, metconazole, difenoconazole, dif cyproconazole, cyproconazole difenoconazole, metconazole, penconazole, difenoconazole and metconazole, Pyrimethanil, mancozeb, copper-compounds (different salts), sulphur, folpet, chlorothalonil, dithianon, propionil, fludioxonil, benzophenone, fluzopyr-diethyl ketone, fluoxazasul-fonate, alac acid benzene-S-methyl, phosphorous acid, cyflufenamid, tricyclazole, N-methoxy-N- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] -cyclopropanecarboxamide, N, 2-dimethoxy-N- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] -propionamide, N- [ (1R) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, n- [ (1S) -1-benzyl-1, 3-dimethyl-butyl ] -8-fluoro-quinoline-3-carboxamide, N- ((1R) -1-benzyl-3-chloro-1-methyl-but-3-enyl) -8-fluoro-quinoline-3-carboxamide, N- ((1S) -1-benzyl-3-chloro-1-methyl-but-3-enyl) -8-fluoro-quinoline-3-carboxamide, methyl (Z) -2- (5-cyclohexyl-2-methyl-phenoxy) -3-methoxy-prop-2-enoate (this compound can be prepared by the method described in WO 2020/193387), 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -5-methyl-N-spiro [3.4] oct-3-yl-thiazole-4-carboxamide, 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (2-methoxyacetyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (tetrahydropyran-4-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (oxetane-3-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (tetrahydrofuran-3-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ acetyl- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, 2- [ (2, 6-difluoro-4-pyridinyl) - (2-methylpropyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide, TAEGRO (i.e., bacillus amyloliquefaciens strain FZB 24), Melaleuca alternifolia oil (melaleuca alternifolia extract of tea plant (commercially available as Timorex Gold, which is a broad-spectrum plant biological fungicide)), polygonum cuspidatum extract (commercially available as REGALIA), a plant extract based on a lycopodium clavatum extract (commercially available as BOTRISTOP), or aureobasidin a, and wherein components (B) and (C) are not the same compound.

More preferably, a fungicidal composition is provided, comprising as active ingredients a mixture of component (a) and component (B) and component (C), wherein component (a) is a compound having formula (I) selected from compounds (x.01), (x.02), (x.03), (x.04), (x.05), (x.06), (x.07), (x.08), (x.09), (x.10), or (x.11), listed in table X according to the invention, and wherein component (C) and component (B) are compounds selected from the group consisting of: fluxapyroxad hydroxylamine, benzovindiflupyr, trifloxystrobin, pyraclostrobin, tetrazolone, picolinamide, fluazinam, fenpropidin, difenoconazole, metconazole, propiconazole, prothioconazole, haloxyfop-butyl, fluxazole, cyprodinil, fludioxonil, N-methoxy-N- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] cyclopropanecarboxamide, N, 2-dimethoxy-N- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] propionamide, or (Z) -2- (5-cyclohexyl-2-methyl-phenoxy) -3-methoxy-prop-2-enoic acid methyl ester, and wherein components (B) and (C) are not the same compound.

Even more preferably, there is provided a fungicidal composition comprising as active ingredients a mixture of component (a) and component (B) and component (C), wherein component (a) is a compound of formula (I) selected from compounds (x.01), (x.02), (x.03), (x.04), (x.05), (x.06), (x.07), (x.08), (x.09), (x.10), or (x.11), listed in table X according to the invention, and wherein component (C) and component (B) are compounds selected from the group consisting of: fluxapyroxad hydroxylamine, benzovindiflupyr, trifloxystrobin, pyraclostrobin, tetrazolone, picolinamide, fluazinam, fenpropidin, difenoconazole, metconazole, propiconazole, prothioconazole, haloxyfop-butyl, fluxazole, cyprodinil, fludioxonil, N-methoxy-N- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] cyclopropanecarboxamide, N, 2-dimethoxy-N- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] propionamide, or (Z) -2- (5-cyclohexyl-2-methyl-phenoxy) -3-methoxy-prop-2-enoic acid methyl ester, and wherein components (B) and (C) are not the same compound.

These component (C) compounds are mentioned herein and hereinabove by way of the so-called "ISO common name" or another "common name" or trade name used in the individual case. These component (C) compounds are known and are commercially available and/or can be prepared using procedures known in the art and/or reported in the literature as indicated above.

The combination of components (B) and (C) with component (A) can enhance the effect of the latter against fungi and vice versa. Furthermore, fungicidal compositions may be effective against a broader spectrum of fungal pathogens, which when used alone may be against individual active ingredients. In general, the weight ratio of component (A) to the mixture of components (B) and (C) may be from 100:1 to 1:100, or 50:1 to 1:50, or 20:1 to 1:20, or 10:1 to 1:10, or 5:1 to 1:5. Otherwise, the weight ratio of component (A) to the mixture of components (B) and (C) may be from 2:1 to 1:2, or 4:1 to 2:1, or 1:1, or 5:1, or 5:2, or 5:3, or 5:4, or 4:1, or 4:2, or 4:3, or 3:1, or 3:2, or 2:1, or 1:5, or 3:5, or 4:5, or 1:4, or 2:4, or 3:4, or 1:3, or 2:3, or 1:2, or 1:600, or 1:300, or 1:150, or 1:35, or 2:35, or 4:35, or 1:75, or 2:75, or 4:75, or 1:6000, or 1:3000, or 1:1500, or 1:350, or 2:350, or 4:350, or 750. Those mixing ratios are understood to include, on the one hand, ratios by weight and, on the other hand, molar ratios as well.

In embodiments of the invention wherein the composition comprises component (A), component (B) and component (C), the weight ratio of component (A) to the sum of component (B) and component (C) may be from 100:1 to 1:100, preferably from 50:1 to 1:50, more preferably from 20:1 to 1:40, even more preferably from 15:1 to 1:30, still more preferably from 12:1 to 1:25, or from 10:1 to 1:20, or from 10:1 to 1:10, or from 5:1 to 1:15, or from 5:1 to 1:5, or from 4:1 to 1:4, or from 3:1 to 1:10, or from 3:1 to 1:3, or from 2:1 to 1:5, or 1:1.

The compounds of formula (I) according to the invention can be manufactured as shown in the following schemes, wherein the definition of each variable is as defined above for the compounds of formula (I) unless otherwise indicated.

The term "compound of formula (I)" refers to component a.

In any of the following schemes, the presence of one or more possible asymmetric carbon atoms in the compounds of formula (I) according to the invention means that these compounds may exist in chiral isomer form, i.e. in enantiomeric or diastereomeric form.

The compounds of formula (I) may be prepared by methods known to those skilled in the art. More specifically, compounds having formula (I) may be prepared from compounds having formula (III) or salts thereof, wherein R ¹、R²、R³、R⁴、R⁵、R⁶、R⁷、X¹、X² and X ³ are as defined above for compounds having formula (I), by reaction with compounds having formula (V), wherein a ¹、A²、A³ and Z ¹ are as defined above for compounds having formula (I). This reaction is shown in scheme 1.

Scheme 1

In scheme 1, a compound of formula (V), wherein a ¹、A²、A³ and Z ¹ are as defined above for a compound of formula (I), is activated to a compound of formula (Va) by methods known to those skilled in the art and described, for example, in Tetrahedron 2005, 61 (46), 10827-10852. For example, compounds having formula (Va) (wherein X ⁰ is halogen) are formed by treating a compound having formula (V) with, for example, oxalyl chloride or thionyl chloride in the presence of a catalytic amount of N, N-Dimethylformamide (DMF) in an inert solvent such as Dichloromethane (DCM) or Tetrahydrofuran (THF) at a temperature from 20 ℃ to 100 ℃, preferably 25 ℃. Treating a compound of formula (Va) with a compound of formula (III) (wherein R¹、R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸、X¹、X² and X ³ are as defined above for a compound of formula (I)) optionally in the presence of a base such as triethylamine or pyridine, to give a compound of formula (I). Alternatively, the catalyst may be prepared by reacting a Dicyclohexylcarbodiimide (DCC) with a solvent selected from the group consisting of pyridine, DMF, acetonitrile, DCM and THF in an inert solvent, optionally in the presence of a base selected from the group consisting of triethylamine, at a temperature of from 30 ℃ to 180 °c, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide (EDC) or 1- [ bis (dimethylamino) methylene ] -1H-1,2, 3-triazolo [4,5-b ] pyridinium-3-oxide Hexafluorophosphate (HATU) treatment of a compound of formula (V) to give an activated compound of formula (Va) (wherein X ⁰ is X ⁰¹、X⁰² or X ⁰³ as described below) to prepare a compound of formula (I). Finally, the compound of formula (V) may also be activated by reaction with a coupling agent such as propane phosphonic anhydride (T3P), providing a compound of formula (Va), wherein X ⁰ is X ⁰⁴ as described below, as described, for example, in Synthesis 2013, 45, 1569. Further reacting with a compound having the formula (III) or a salt thereof to obtain a compound having the formula (I).

The compounds of formula (IIIa) wherein R ⁴ and R ⁶ are hydrogen, R ⁵ is hydrogen or methyl and R ¹、R²、R³、R⁷、X¹、X² and X ³ are as defined above for compounds of formula (I) can be prepared by one skilled in the art according to known methods.

For example, compounds of formula (IIIa) wherein R ⁴ and R ⁶ are hydrogen, R ⁵ is hydrogen or methyl and R ¹、R²、R³、R⁷、X¹、X² and X ³ are as defined above for compounds of formula (I) can be prepared from compounds of formula (IVa) wherein R ⁵ is hydrogen or methyl and R ¹、R²、R³、R⁷、X¹、X² and X ³ are as defined above for compounds of formula (I) by treatment with a reducing agent (e.g., naBH ₃ CN) and an acid (e.g., hydrochloric acid, or acetic acid) in a protic solvent (e.g., methanol or ethanol, etc.). Such reactions are well known in the literature and similar reactions have been described, for example, in Deng, zeping et al, CN103772278 and Synthesis [ Synthesis ] (1979), 4, 281-3. Alternatively, compounds having formula (IIIa) may be prepared from compounds having formula (IV) by reduction with hydrogen in the presence of a suitable metal catalyst (e.g. Pd, ir, rh) with a suitable ligand (e.g. diphosphine [1, 2-bis (diphenylphosphino) ethane (dppe), 1, 3-bis (diphenylphosphino) propane (dppp) or 1, 4-bis (diphenylphosphino) butane (dppb) ]). Similar reactions have been reported, for example, in compact, kine, catalyst, lett [ reaction kinetics and catalysis flash ] 2007, 92, 99-104 (scheme 2).

Scheme 2

Alternatively, compounds having formula (IIIa) may be prepared as shown in scheme 4.

As shown in scheme 3, compounds having formula (IIIb) (wherein R ⁴、R⁶ and R ⁷ are hydrogen, R ⁵ is hydrogen or methyl and R ¹、R²、R³、X¹、X² and X ³ are as defined above for compounds having formula (I)) can be converted to compounds having formula (VII) (wherein R ⁴、R⁶ and R ⁷ are hydrogen, R ⁵ is hydrogen or methyl and R ¹、R²、R³、X¹、X² and X ³ are as defined above for compounds having formula (I)) by treatment with compounds having formula (VI) (wherein X ⁰ is a leaving group, such as halogen, and R ⁰ is C ₁-C₄ -alkyl) by methods known to those skilled in the art and by methods described in scheme 1. alternatively, the compound of formula (VII) may be prepared by treatment with an anhydride of formula (R ⁰CO)₂ O wherein R ⁰ is C ₁-C₄ -alkyl) in an inert solvent such as DCM, THF or 2-methyl-THF, optionally in the presence of a base such as triethylamine or dimethylaminopyridine, at a temperature between 0 ℃ and 60 ℃. The compound of formula (VII) is then metallized with a base (e.g., a metal alkyl base such as t-butyllithium) and an additive such as N, N' -tetramethyl ethylenediamine (TMEDA)) in an inert polar solvent such as THF or 2-methyl-THF at low temperature (e.g., from-78 ℃ to room temperature). Followed by the use of an electrophile having the formula R ^X-X⁰ (wherein X ⁰ is as previously defined and R ^X is C ₁-C_4- alkyl, C ₁-C_4- Alkylcarbonyl, C ₁-C_4- alkoxycarbonyl, N-methoxy-N-methyl-carbonyl, C ₁-C_4- alkylaminocarbonyl, di (C ₁-C_4- alkyl) aminocarbonyl or C ₃-C_6- cycloalkyl, wherein the C ₃-C₆ -cycloalkyl is optionally substituted with 1, 2 or 3 are independently selected from halogen, cyano, C ₁-C₄ -alkyl, The substitution of the substituents of C ₁-C₄ -haloalkyl and C ₁-C₄ -alkoxy) to the anion of formula (VII) formed under such conditions gives the compound of formula (VIIa) (wherein R ⁴ and R ⁶ are hydrogen, R ⁵ is hydrogen or methyl, R ⁰ is C ₁-C₄ -alkyl and R ¹、R²、R³、R⁷、X¹、X² and X ³ are as defined above for the compound of formula (I) (scheme 3).

Scheme 3

The compounds of formula (VIIa) may be converted to compounds of formula (IIIa) by methods known to those skilled in the art (wherein R ⁴ and R ⁶ are hydrogen, R ⁵ is hydrogen or methyl, and R ¹、R²、R³、R⁷、X¹、X² and X ³ are as defined above for compounds of formula (I)). For example, a compound having formula (VIIa) wherein R ⁰ is t-butyl may be treated with an organic or inorganic acid such as trifluoroacetic acid or HCl to provide a compound having formula (IIIa). This reaction is shown in scheme 4.

Scheme 4

The compounds of formula (IVa) wherein R ⁵ is hydrogen or methyl and R ¹、R²、R³、R⁷、X¹、X² and X ³ are as defined above for the compounds of formula (I) can be prepared by reacting a compound of formula (IX) wherein R ¹、R² and R ³ are as defined above for the compounds of formula (I) and X ⁰ is halogen, preferably chlorine, bromine or iodine, with a compound of formula (VIII) wherein R ⁵ is hydrogen or methyl and R ⁷、X¹、X² and X ³ are as defined above for the compounds of formula (I) by means of a C-C bond formation reaction, typically under palladium-catalyzed (alternatively nickel-catalyzed) cross-coupling conditions (scheme 5).

Scheme 5

The Suzuki-Miyaura cross-coupling reaction between a compound of formula (VIII) and a compound of formula (IX) is well known to the person skilled in the art and is typically carried out in the presence of a palladium catalyst such as tetrakis (triphenylphosphine) -palladium (0) or [1,1' -bis (diphenylphosphino) ferrocene ] palladium (II) dichloride dichloromethane complex and a base such as sodium carbonate or potassium carbonate in a solvent such as N, N-dimethylformamide, dioxane or dioxane-water mixtures at a temperature between room temperature and 160 ℃, optionally under microwave heating conditions, and preferably under an inert atmosphere. Such reactions have been reviewed in, for example, J.Organomet.Chem. [ journal of organometallic chemistry ] 1999, 576, 147-168. Those skilled in the art will also recognize that the reaction may be reversed, i.e., by reacting a compound of formula (XI) wherein R ¹、R² and R ³ are as defined above for a compound of formula (I) with a compound of formula (X) wherein R ⁵ is hydrogen or methyl, R ⁷、X¹、X² and X ³ are as defined above for a compound of formula (I), and X ⁰ is halogen, preferably chlorine, bromine or iodine, to provide a compound of formula (IVa) wherein R ⁵ is hydrogen or methyl, and R ¹、R²、R³、R⁷、X¹、X² and X ³ are as defined above for a compound of formula (I). This reaction is shown in scheme 6.

Scheme 6

Additional cross-coupling chemistry (i.e., C-H activation) can also be used to prepare compounds having formula (IVa) (wherein R ⁵ is hydrogen or methyl, and R ¹、R²、R³、R⁷、X¹、X² and X ³ are as defined above for compounds having formula (I)). This reaction is shown in scheme 7.

Scheme 7

As shown in scheme 7, a compound of formula (X) wherein R ⁵ is hydrogen or methyl, R ⁷、X¹、X² and X ³ are as defined above for a compound of formula (I), and X ⁰ is halogen, preferably chlorine, bromine or iodine, is reacted with a compound of formula (XII) wherein R ¹、R² and R ³ are as defined above for a compound of formula (I) in the presence of a palladium catalyst, typically palladium acetate Pd (OAc) ₂, a suitable ligand, e.g. 1, 10-phenanthroline, in the presence of a base, such as cesium carbonate or potassium carbonate, in an inert solvent, such as chlorobenzene, toluene or xylene, at a temperature between room temperature and 180 ℃, optionally under microwave heating conditions, preferably under an inert atmosphere. Similar reactions have been reported in literature such as chem. Sci. [ chemistry sciences ] 2013, 4, 2374-2379.

In addition, compounds having formula (III) may be prepared from compounds having formula (XIII) (scheme 8).

Scheme 8

As shown in scheme 8, compounds having formula (III) can be prepared by one skilled in the art by carbamate deprotection reactions of compounds having formula (XIII) wherein R ¹、R²、R³、R⁴、R⁵、R⁶、R⁷、X¹、X² and X ³ are as defined above for compounds having formula (I), and R ⁰¹ can be a member of a common carbamate protecting group substituent, such as methyl, t-butyl, allyl, 2-trichloroethyl, or benzyl. For example, when R ⁰¹ is methyl, a suitable solvent (e.g., methylene chloride) and a suitable reagent (e.g., iodotrimethylsilane) may be employed to provide the product when heated at a temperature between room temperature and 200 ℃, preferably between 20 ℃ and the boiling point of the reaction mixture, as described, for example, in j. Am. chem. Soc. [ american society of chemistry ] 1992, 114, 5959. As shown in scheme 1, the compound of formula (III) thus obtained is converted into a compound of formula (I).

Compounds of formula (XIII), wherein R ¹、R²、R³、R⁴、R⁵、R⁶、R⁷、X¹、X² and X ³ are as defined above for compounds of formula (I), and wherein R ⁰¹ is as described above, can be formed by combining an aldehyde of formula (XV), including formaldehyde in its different forms, wherein R ⁷ is as defined above for compounds of formula (I), with a compound of formula (XIV), wherein R ¹、R²、R³、R⁴、R⁵、R⁶、X¹、X² and X ³ are as defined above for compounds of formula (I), and wherein R ⁰¹ is as described above, by reacting with an acid in a suitable solvent, for example as described in Tetrahedron [ Tetrahedron ] 1987, 43, 439. This reaction is shown in scheme 9.

Scheme 9

The compounds of formula (XIV) wherein R ¹、R²、R³、R⁴、R⁵、R⁶、X¹、X² and X ³ are as defined above for compounds of formula (I) and wherein R ⁰¹ is as described above, may be prepared by reaction between an amine of formula (XVI) wherein R ¹、R²、R³、R⁴、R⁵、R⁶、X¹、X² and X ³ are as defined above for compounds of formula (I) and a suitable protecting agent such as methyl chloroformate, as described, for example, in org, biomlect chem [ organic and biomolecular chemistry ] 2016, 14, 6853, optionally in the presence of a base such as triethylamine or pyridine, in a suitable solvent such as dichloromethane, at a temperature between-20 ℃ and the boiling point of the mixture. This reaction is shown in scheme 10.

Scheme 10

The compounds of formula (XVI) or salts thereof, wherein R ¹、R²、R³、R⁴、R⁵、R⁶、X¹、X² and X ³ are as defined above for compounds of formula (I), can be prepared by one skilled in the art by reaction between a nitrile of formula (XVII), wherein R ¹、R²、R³、R⁴、X¹、X² and X ³ are as defined above for compounds of formula (I), and a suitable nucleophile, such as (dimethyl sulfide) boron dihydrogen (BMS), in a suitable aprotic solvent, such as THF, for example as described in j.org. chem. [ journal of organic chemistry ] 1981 47, 3153. Alternatively, grignard reagent R ⁵ MgBr or R ⁶ MgBr, wherein R ⁵ and R ⁶ are as defined above for compounds of formula (I), may be added to compounds of formula (XVII) sequentially or simultaneously as nucleophiles to allow the preparation of more highly substituted amines of formula (XVI). Such grignard addition to nitriles (see Synlett 2007, (4), 652-654) is carried out in the presence of lewis acids such as Ti (O- ⁱPr)₄) in inert solvents such as diethyl ether, t-butyl methyl ether and cyclopentyl methyl ether.

Scheme 11

The compounds of formula (XVII), wherein R ¹、R²、R³、R⁴、X¹、X² and X ³ are as defined above for compounds of formula (I), can be prepared by a person skilled in the art according to known methods. More specifically, compounds having formula (XVII) and intermediates thereof can be prepared from compounds having formula (XVIII), as shown in scheme 12.

Scheme 12

For example, compounds having formula (XVII) wherein R ¹、R²、R³、R⁴、X¹、X² and X ³ are as defined above for compounds having formula (I) and R ⁴ is not hydrogen, can be prepared by one skilled in the art by deprotonation of compounds having formula (XVIIa) wherein R ⁴ is hydrogen and R ¹、R²、R³、X¹、X² and X ³ are as defined above for compounds having formula (I) using a strong base such as n-butyllithium or sodium hydride in an inert solvent such as THF at low temperature followed by the addition of a suitable alkylating agent R ⁴ -X wherein X is halogen such as methyl iodide.

The compound of formula (XVIIa), wherein R ⁴ is hydrogen and R ¹、R²、R³、X¹、X² and X ³ are as defined above for the compound of formula (I), can be prepared from an alcohol of formula (XVIII) by treatment with a cyano Trimethylsilane (TMSCN) in the presence of a base such as lithium carbonate in a non-polar solvent such as dichloromethane at a temperature between 0 ℃ and the boiling point of the reaction mixture. Such transformations are well known in the literature under a variety of conditions, for example as described in org, lett [ organic flash report ] 2008, 10, 4570 and references therein. This reaction is shown in scheme 12.

The compounds of formula (III) are commercially available or are readily prepared by compounds known in the art. The compounds of formula (XVIII) can be prepared by methods known to those skilled in the art.

The compounds of formula (I) as defined in any of the embodiments of the invention may be converted in a manner known per se into another compound as defined in any of the embodiments of the invention by replacing one or more substituents of the starting compounds with another or other substituents according to the invention in a conventional manner. Those skilled in the art will also appreciate that the compounds of formula (I) may be further converted into additional derivatives of formula (I) by, for example, alkylation, nucleophilic substitution, elimination, C-C bond formation reactions in the presence of a metal catalyst, heteroatom-carbon bond formation in the presence of a metal catalyst, oxidation and reduction.

Depending on the reaction conditions selected as appropriate 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 to replace a plurality of substituents with other substituents according to the invention in the same reaction step.

Salts of the compounds of formula (I) may be prepared in a manner known per se. Thus, for example, the acid addition salts of the compounds of formula (I) 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 with a suitable ion exchange reagent.

Salts of the compounds of formula (I) can be converted in a conventional manner to the free compounds (I), acid addition salts (e.g. by treatment with suitable basic compounds or with suitable ion exchange reagents) and salts with bases (e.g. by treatment with suitable acids or with suitable ion exchange reagents).

Salts of the compounds of formula (I) can be converted in a manner known per se into other salts, acid addition salts, for example into other acid addition salts, of the compounds of formula (I), for example by treating salts of inorganic acids, such as hydrochloride salts, with suitable metal salts of acids, such as salts of sodium, barium or silver, for example with silver acetate, in a suitable solvent in which the inorganic salts formed, such as silver chloride, are insoluble and thus precipitate out of the reaction mixture.

Depending on the procedure or the reaction conditions, the compounds of formula (I) having salifying properties can be obtained in free form or in salt form.

The compounds of the formula (I) and, where appropriate, the tautomers thereof (in each case in free form or in salt form) may be present in the form of one of the possible isomers or as mixtures of these isomers, for example in the form of pure isomers (such as enantiomers and/or diastereomers) or as mixtures of isomers (such as mixtures of enantiomers, for example racemates, or mixtures of diastereomers), depending on the number, absolute and relative configuration of the asymmetric carbon atoms present in the molecule and/or on the configuration of the non-aromatic double bonds present in the molecule, the invention relates to pure isomers and also to all possible mixtures of isomers, and in each case to the context even in each case without specific reference to stereochemical details, should be understood in this sense.

Diastereomeric mixtures or racemate mixtures of compounds of the formula (I) in free form or in salt form, which may be obtained depending on the starting materials and procedures selected, may be separated into the pure diastereomers or racemates in a known manner on the basis of the physicochemical differences of these components, for example by fractional crystallization, distillation and/or chromatography.

Mixtures of enantiomers (such as racemates) which can be obtained in a similar manner can be resolved into the optical enantiomers by known methods, for example by recrystallisation from optically active solvents, by chromatography on chiral adsorbents, for example by High Performance Liquid Chromatography (HPLC) on acetyl cellulose, by cleavage with specific immobilized enzymes by means of suitable microorganisms, by formation of inclusion compounds, for example using chiral crown ethers, in which only one enantiomer is complexed, or by conversion into salts of diastereomers, for example by reaction of the basic end product racemate with optically active acids (such as carboxylic acids, for example camphoric acid, tartaric acid or malic acid, or sulphonic acids, for example camphoric acid), and separation of the mixtures of diastereomers which can be obtained in this way, for example by fractional crystallisation on the basis of their different solubilities, whereby the desired enantiomer can be freed from these diastereomers by the action of suitable reagents (for example basic reagents).

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

If the individual components have different biological activities, it is advantageous to separate or synthesize in each case the biologically more effective isomers, for example enantiomers or diastereomers or isomer mixtures, for example enantiomer mixtures or diastereomer mixtures.

As an example, compounds having more than one asymmetric carbon atom may exist in diastereoisomeric form, which may optionally be separated using, for example, supercritical Fluid Chromatography (SFC) chromatography with chiral columns. Such diastereomers may show different fungicidal activity characteristics, but all isomers and diastereomers form part of the present invention.

The compounds of the invention of formula (I) (also shown for compounds of formula (I-A)) exhibit two asymmetric carbon atoms, wherein the asterisks [ ]) An asymmetric carbon atom is indicated, so there are four stereoisomers available. These four stereoisomers consist of two sets of enantiomers.

Those skilled in the art will readily appreciate that the diastereomers and enantiomers of formula (I) and (I-a) described above, wherein R¹、R²、R³、R⁴、R⁵、R⁶、R⁷、X¹、X²、X³、A and Z ¹ are as defined for formula (I), are within the scope of the invention.

The relationship between enantiomers and diastereomers of compounds having formula (I-a) is shown below, wherein R ¹ is methyl, R ² and R ⁴ are hydrogen, R ⁷ is methyl, X ¹ and X ² are CH, X ³ is S, and a is A9.

The compounds of the formula (I) and, where appropriate, the tautomers thereof (in each case in free form or in salt form) can also, if appropriate, be obtained in the form of hydrates and/or include other solvents, for example those which can be used for crystallizing compounds which are present in solid form.

The compositions according to the invention are effective against harmful microorganisms (such as microorganisms) causing phytopathogenic diseases, in particular against phytopathogenic fungi and bacteria.

The compositions of the invention may be used to control plant diseases caused by a broad spectrum of fungal plant pathogens in basidiomycetes (Basidiomycete), ascomycetes (ascomycetes), oomycetes (Oomycete) and/or semi-known mycoplasmas (Deuteromycete), lophatherum (Blasocladiomycete), chytrium (Chrytidiomycete), sacculus fungi (Glomeromycete) and/or mucorales (Mucoromycete).

The composition is effective in controlling a broad spectrum of plant diseases such as foliar pathogens of ornamental plants, turf, vegetables, fields, cereals, and fruit crops.

These pathogens may include oomycetes, including phytophthora, such as those caused by phytophthora capsici, phytophthora infestans, phytophthora sojae, strawberry phytophthora (Phytophthora fragariae), phytophthora nicotianae (Phytophthora nicotianae), phytophthora camphorax (Phytophthora cinnamomi), phytophthora citri reticulatae (Phytophthora citricola), phytophthora citri reticulatae (Phytophthora citrophthora) and potato Pythium (Phytophthora erythroseptica), pythium, such as those caused by Pythium citrulli, pythium Jiang Xiong (Pythium arrhenomanes), pythium gracile, pythium irregulare (Pythium irregulare) and Pythium ultimum, those caused by the order of the order peronosporales such as downy mildew (Peronospora destructor), downy mildew of chinese cabbage, downy mildew of grape, downy mildew, cucumber downy mildew, white rust (Albugo candida), rice downy mildew and lettuce basidium, and others such as myceliophthora spirochete, lawsonia Lin Sula zoteichum (Labyrinthula zosterae), pythium gracile (Peronosclerospora sorghi) and Pythium gracile (Sclerospora graminicola);

Ascomycetes, including spot, leaf spot, blast or epidemic disease and/or rot, such as those caused by Gramineae, e.g., alternaria alliacea (Stemphylium solani), narcissus tainanensis (Stagonospora tainanensis), cyclosporium oleae, alternaria corn (Setosphaeria turcica), equisqualis (Pyrenochaeta lycoperisici), alternaria alternata, phoma solid (Phoma destructiva), cytospora fuliginea, Wheat She An coccidioides (Phaeosphaeria herpotrichoides), gao Manni Cryptococcus palmatus (Phaeocryptocus gaeumannii), snake spore intracavity (Ophiosphaerella graminicola), snake spore intracavity (Ophiobolus graminis), cruciferae globus (Leptosphaeria maculans), soft rot fungus (Hendersonia creberrima), needle-leaved blight fungus (Helminthosporium triticirepentis), Corn porus (Setosphaeria turcica), soybean inner navel vermicularia (DRECHSLERA GLYCINES), melon agana spore shell (DIDYMELLA BRYONIAE), olive peacock spot germ (Cycloconium oleagineum), multi-main coryneform bacterium, alternaria graminea, dragon fruit black spot germ (Bipolaris cactivora), apple scab bacterium (Venturia inaequalis), nuclear cavity bacterium (Pyrenophora teres), myriopsis (Pyrenophora tritici-repentis), alternaria alternata (ALTERNARIA ALTERNATA), alternaria brassicae (ALTERNARIA BRASSICICOLA), alternaria solani and Alternaria tomato (ALTERNARIA TOMATOPHILA), and Leptosphaeria (Capnodiales) of order coal (Capnodiales) such as Septoria tritici, septoria nodorum (Septoria nodorum), septoria sojae (Septoria glycines), Cercospora arachidicola (Cercospora arachidicola), cercospora sojae, cercospora zeae, cercospora shepherdspurse (Cercosporella capsellae), wheat She Baimei (Cercosporella herpotrichoides), cercospora persicae (Cladosporium carpophilum), amycolatopsis (Cladosporium effusum), brown spore mold (Passalora fulva), amycolatopsis (Cladosporium oxysporum), and other plant species, Needle-base ascomycetes (Dothistroma septosporum), brown spot grape bacteria (Isariopsis clavispora), fijia globeflower bacteria (Mycosphaerella graminicola), chaetomium longum (Mycovellosiella koepkeii), sweet potato phomopsis (Phaeoisariopsis bataticola), brown spot grape bacteria (Pseudocercospora vitis), Cercospora (Pseudocercosporella herpotrichoides), cercospora spinosa (Ramularia collo-cygni), leptosphaeria, gramineae such as Pyricularia graminea, pyricularia oryzae (Magnaporthe grisea), pyricularia oryzae, gekko Swinhonis such as Alternaria lunata, apiognomonia errabunda, mortierella jenkinii (Cytospora platani), cynanchum phaseoli (Diaporthe phaseolorum), The plant species comprise, by weight, destroyed sedum (Discula destructiva), japanese calicheapest strawberry (Gnomonia fructicola), pholiota nameko, black calico walnut (Melanconium juglandinum), phomopsis viticola (Phomopsis viticola), phoma juglandis (Sirococcus clavigignenti-juglandacearum), conidium kansui (Tubakia dryina), geopepera species (DICARPELLA spp.), and, Apple tree rot germ (Valsa ceratosperma), and others such as Actinothyrium graminis, aschersonia pea, aspergillus flavus, aspergillus fumigatus, aspergillus nidulans, aspergillus papaya, phyllosphaera (Blumeriella jaapii), candida species, soot germ (Capnodium ramosum), sirtuin Luo Suoka species (Cephaloascus spp.), alternaria maculata (Cephalosporium gramineum), Coracoid (Ceratocystis paradoxa), chaetomium species, sphaeria species (Hymenoscyphus pseudoalbidus), coccidioides species, pillarium species (Cylindrosporium padi), bivalve (Diplocarpon malae), pennywort (Drepanopeziza campestris), elsino-elsino (Elsinoe ampelina), epicoccum nigrum, epidermophyton species, curvularia vitis (Eutypa lata), and, Geotrichum candidum, leptoradix Gramineae housing (Gibellina cerealis), cyamopsis johnsonii (Gloeocercospora sorghi), leptosporum crenatum (Gloeodes pomigena), leptosporum perennium (Gloeosporium perennans), endophytic fungi of Porphyra tenebrio (Gloeotinia temulenta), leptosporum album (Griphospaeria corticola), leptosporum Li Niqiu (Kabatiella lini), leptosporum microsporium (Leptographium microsporum), leptosporum (Leptographium microsporum), The preparation method comprises the steps of preparing a sorrel (Leptosphaerulinia crassiasca), a disturbing speckle shell (Lophodermium seditiosum), a grass Gu Pan bipolaris (Marssonina graminicola), a snow mold leaf blight (Microdochium nivale), a Meinao stone fruit brown rot germ (Monilinia fructicola), a rice cloud shape disease (Monographella albescens), a melon black spot root rot germ (Monosporascus cannonballus), The species of the genus Sp (Naemacyclus spp.), new Ulmilum (Ophiostoma novo-ulmi) paracoccidiosis brazil (Paracoccidioides brasiliensis), penicillium expansum (Penicillium expansum) Mucor rhodochrous (Pestalotia rhododendri), petrenia species (Petriellidium spp.), pantoea species (Pezicula spp.), petrenia species, Brown rot germ (Phialophora gregata) of soybean stem, black nevus (Phyllachora pomigena) of kernel fruit, tumor pedunculata (Phymatotrichum omnivora) of omnivora, cryptosporidium (Physalospora abdita), aschersonia (Plectosporium tabacinum), potato leaf spot germ (Polyscytalum pustulans), pseudodish alfalfa (Pseudopeziza medicaginis), Sclerotinia brassicae (Pyrenopeziza brassicae), aschersonia sorghum (Ramulispora sorghi), douglas fir fan She Bingjun (Rhabdocline pseudotsugae), pholiota nameko (Rhynchosporium secalis), cladosporium cucumerinum (Sacrocladium oryzae), podophyllum species (Scedosporium spp.), apple coal point germ (Schizothyrium pomi), and, Sclerotinia sclerotiorum (Sclerotinia sclerotiorum), sclerotinia sclerotiorum (Sclerotinia minor), sclerotinia species (Sclerotium spp.), ramaria snow rot (Typhula ishikariensis), maban Makino (Seimatosporium mariae), curvularia arborescens (Lepteutypa cupressi), alternaria purpurea (Septocyta ruborum), pyricularia avocado scab (Sphaceloma perseae), rake, The plant may be selected from the group consisting of alfalfa branch and stem edge-cracking (Sporonema phacidioides), millennia jujube eye-spot germ (Stigmina palmivora), tappe Siemens di (Tapesia yallundae), pear exocyst (Taphrina bullata), cotton black root rot germ (Thielviopsis basicola), tricks Li Yafu Lu Diji na (Trichoseptoria fructigena), fly feces germ (Zygophiala jamaicensis), powdery mildew such as from the order of powdery mildew such as Blumeria brucei (Blumeria graminis), Powdery mildew of Polygonum tinctorium, uncaria grape shells, erysiphe cucumeris (Sphaerotheca fuligena), leptospira graminis, erysiphe alternifera (Podospaera macularis), erysiphe bisporus (Golovinomyces cichoracearum), erysiphe taurica (Leveillula taurica), leptospira diffusa, alternaria gossypii (Oidiopsis gossypii), corylus hazel needle shells (PHYLLACTINIA GUTTATA) and Alternaria groundnut (Oidium arachidis), mildew, for example from Siberian fungi such as Aphanotheca pareinkinensis (Dothiorella aromatica), Saccharopolyspora crassa (Diplodia seriata), bryonia bivaliae (Guignardia bidwellii), botrytis cinerea, succinum (Botryotinia allii), succinum falcatum (Botryotinia fabae), clostridium amygdalium (Fusicoccum amygdali), pyricularia longan (Lasiodiplodia theobromae), phoma tea (Macrophoma theicola), rhizopus oryzae (Macrophoma theicola), Alternaria phaseoloides, leptosphaeria cucurbitaceae (Phyllosticta cucurbitacearum), anthrax, e.g., those caused by small plexus shells (Glommerelales) such as Leptosphaeria, aphaeus anthracnose (Colletotrichum lagenarium), leptosphaeria gossypii, leptosphaeria, and Leptosphaeria graminea, and fusarium, e.g., acremonium straight, virgotomyces, fusarium flavum, fusarium graminearum, tacrolimus sojae (Fusarium virguliforme), tacrolimus, Fusarium oxysporum, fusarium mucilaginosum, fusarium culmorum (Fusarium oxysporum f.sp. cubense), george nikoense (GERLACHIA NIVALE), gibberella vinifera, gibberella zeae, cladosporium, myrothecium verrucosum, laura Lei Congchi shellac (Nectria ramulariae), trichoderma viride, leptosporum rubrum, and Rhizoctonia avocado (Verticillium theobromae);

Basidiomycetes, including smut, such as those caused by ustilaginoidea, e.g., ustilago oryzae (Ustilaginoidea virens), barley smut (Ustilago nuda), wheat smut (Ustilago tritici), corn smut (Ustilago zeae), rust, e.g., by rust, e.g., rust fig (Cerotelium fici), rust spruce (Chrysomyxa arctostaphyli), sweet potato sheath rust (Coleosporium ipomoeae), Alternaria caffei (Hemileia vastatrix), alternaria arachnoidis (Puccinia arachidis), alternaria southwest (Puccinia cacabata), alternaria graminea (Puccinia graminis), alternaria secoisolaris (Puccinia recondita), alternaria sorghum (Puccinia sorghi), alternaria barley (Puccinia hordei), alternaria bardansis (Puccinia striiformis f.sp.Hordei), Leptospira tritici (Puccinia striiformis f.sp.Secalis), leptospira filberti (Pucciniastrum coryli), or Leptospira farinacea (Cronartium ribicola), leptospira sabinensis (Gymnosporangium juniperi-virginianae), leptospira populi (Melampsora medusae), leptospira meyenii (Phakopsora pachyrhizi), leptospira meyenii (Pucciniastrum coryli), Polychaetomium breve (Phragmidium mucronatum), polychaetomium ampelopsis (Physopella ampelosidis), leuconostoc mesenteroides (Tranzschelia discolor), leuconostoc mesenteroides (Uromyces viciae-fabae), and other rot and disease, such as those caused by Cryptococcus species (Cryptococcus spp.), alternaria (Exobasidium vexans), leuconostoc mesenteroides (Marasmiellus inoderma), leuconostoc mesenteroides (Amycolata), Pleurotus species (Mycena spp.), head smut (Sphacelotheca reiliana), xuefuzhu nucleus CD (Typhula ishikariensis), leuconostoc sphaeroides (Urocystis agropyri), fabricius (Itersonilia perplexans), neisseria thenium Fu Gejun (Corticium invisum), phanerochaete licheniformis (LAETISARIA FUCIFORMIS), phanerochaete chrysosporium (WAITEA CIRCINATA), phanerochaete chrysosporium, Those caused by rhizoctonia solani (Rhizoctonia solani), coriolus meloidogyne (Thanetephorus cucurmeris), nigella dahliae (Entyloma dahliae), nigella microsporidiana (Entylomella microspora), nigella limosa (Neovossia moliniae) and tiepia graminea (TILLETIA CARIES);

the class Rhizopus, such as Arthropoda zeae (Physoderma maydis);

Mucor, such as Guanyuan (Choanephora cucurbitarum), mucor species, rhizopus arrhizus;

along with diseases caused by other species and genera closely related to those listed above.

In addition to their fungicidal activity, these compositions may also have activity against bacteria such as erwinia amylovora, erwinia soft rot (Erwinia caratovora), xanthomonas campestris, pseudomonas syringae, potato scab (Strptomyces scabies) and other related species, along with certain protozoa.

The compositions according to the invention are particularly effective against phytopathogenic fungi belonging to the classes of the class of the groups Zonospora (e.g. Ceriporia, cercospora, leptosphaeria), of the class Basidiomycetes (e.g. Tech. Rust (Hemileia), rhizoctonia, rhizopus, leptosphaeria, tilletia), of the class of the fungi (also known as Deuteromycetes; e.g. Botrytis, leptosphaeria, corallospora, fusarium, septoria, cercospora, alternaria, pyricularia and Pseudocercospora), of the class of the classes Zostereum (e.g. Phytophthora, peronospora, pseudoperonospora, leptosphaeria, monilium).

Useful plant crops in which the compositions according to the invention can be used include perennial and annual crops, such as berry plants, for example blackberry, blueberry, cranberry, raspberry and strawberry; cereals, such as barley, maize (corn), millet, oat, rice, rye, sorghum, triticale and wheat; fiber plants, such as cotton, flax, hemp, jute and sisal; field crops, such as sugar beet and fodder beet, coffee beans, hops, mustard, rape (canola), poppy, sugarcane, sunflower, tea and tobacco, fruit trees, such as apple trees, apricot trees, avocado trees, banana trees, cherry trees, citrus trees, peach trees, pear trees and plum trees, grasses, such as bermuda grass, bluegrass, bunte grass, centipede, cow's grass, ryegrass, holy-grass and zoysia, herbs, such as basil, borage, chives, coriander, lavender, heracleum hemsleyanum michaux, mint, oregano, parsley, rosemary, sage and thyme, beans, such as beans, lentils, peas and soybeans, nuts, such as almonds, cashew nuts, peanuts, pecans, pistachios and walnuts, palm plants, such as palm, flowers, wood and trees, other trees, such as cocoa, olive trees, and rubber trees, such as lettuce, such as potatoes, lettuce, garcinquefoil, vegetables, potatoes, garbanjo, cucumbers, cucurbits, carrots, potatoes, garcinia, and the like.

Crops are understood to be those which occur naturally, are obtained by conventional breeding methods or are obtained by genetic engineering. They include crops with so-called output traits (e.g. improved storage stability, higher nutritional value and improved flavour).

Crops are understood to also include those crops which have been rendered tolerant to herbicides like bromoxynil or classes of herbicides like ALS-, EPSPS-, GS-, HPPD-and PPO-inhibitors. An example of a crop that has been rendered imidazolinone (e.g., imazethapyr) resistant by conventional breeding methods is Clearfield summer canola. Examples of crops that have been rendered tolerant to herbicides by genetic engineering methods include, for example, glyphosate and glufosinate resistant corn varieties commercially available under the trade names rounduepady, herculex I and LibertyLink.

Crops are also understood as being those crops which are naturally or have been rendered resistant to harmful insects. This includes plants transformed by using recombinant DNA techniques, for example, to synthesize one or more selectively acting toxins, as are known from, for example, toxin-producing bacteria. Examples of toxins that may be expressed include delta-endotoxins, vegetative insecticidal proteins (Vip), insecticidal proteins of nematode parasitic bacteria, and toxins produced by scorpions, arachnids, wasps, and fungi.

An example of a crop that has been modified to express a bacillus thuringiensis toxin is Bt maize KnockOut (seed company (SYNGENTA SEEDS)). An example of a crop comprising more than one gene encoding insecticidal resistance and thereby expressing more than one toxin is VipCot (seed company). The crop or seed material thereof may also be resistant to multiple types of pests (so-called superposition transgenic events when produced by genetic modification). For example, plants may have the ability to express insecticidal proteins while being tolerant to herbicides, such as Herculex I (Tao Shiyi agriculture company (Dow AgroSciences), pioneer stock International company (Pioneer Hi-Bred International)).

The term "useful plant" is to be understood as also including useful plants which have been so transformed by use of recombinant DNA technology that they are capable of synthesizing one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria, especially those of the genus bacillus.

Examples of such plants are YIELDGARD (maize variety, expressing CryIA (B) toxins); YIELDGARD ROOTWORM (maize variety, expressed CryIIIB (B1) toxin), YIELDGARD PLUS (maize variety, expressed CryIA (B) and CryIIIB (B1) toxins), starlink (maize variety, expressed Cry9 (c) toxin), herculex I (maize variety, expressed CryIF (a 2) toxin and enzyme phosphinothricin N-acetyltransferase (PAT) that acquires resistance to the herbicide phosphinothricin salt), nuCOTN B (cotton variety, expressed CryIA (c) toxin), bollgard I (cotton variety, expressed CryIA (c) toxin), bollgard II (cotton variety, expressed CryIA (c) and CryIIA (B) toxin), VIPCOT (cotton variety, expressed VIP toxin), newLeaf (potato variety, expressed CryIIIA toxin), natureGard (Agrisure) (GA GT ADVANTAGE (21) glyphosate resistant), agrisure (Bt CB 11) and maize insect 38 (38.

The term "crop" is to be understood as also including crop plants which have been so transformed by the use of recombinant DNA technology that they are capable of synthesizing one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria, especially those of the genus bacillus.

Toxins that can be expressed by such transgenic plants include, for example, insecticidal proteins from bacillus cereus or bacillus thuringiensis; or insecticidal proteins from bacillus thuringiensis, such as delta-endotoxins, e.g., cry1Ab, cry1Ac, cry1F, cry Fa2, cry2Ab, cry3A, cry Bb1 or Cry9C, or vegetative insecticidal proteins (Vip), e.g., vip1, vip2, vip3 or Vip3A; or bacterial plant-fixing nematicidal proteins, for example, the Photorhabdus species (Photorhabdus spp.) or the Xenorhabdus species (Xenorhabdus spp.), such as, for example, the light-emitting bacilli (Photorhabdus luminescens), the Xenorhabdus nematophilus (Xenorhabdus nematophilus), toxins produced by animals, such as, for example, scorpions, spider toxins, bee toxins and other insect-specific neurotoxins, toxins produced by fungi, such as, for example, streptomycins, plant lectins (lecins), such as, for example, pea lectins, barley lectins or snowflake lectins, lectins (agglutinin), protease inhibitors, such as trypsin inhibitors, silk protease inhibitors, potato glycoproteins, cystatin, papain inhibitors, ribosome-inactivating proteins (RIP), such as, for example, ricin, corn-RIP, abrin, luffa seed toxin, saporin or heterologous mycotoxin, steroid metabolizing enzymes, such as 3-hydroxysteroid oxidase, ecdysone-UDP-glycosyltransferase, cholesterol oxidase, ecdysone, HMG-COA-reductase, sodium channel, or a channel, a vitamin, a synthase receptor, a lipase, a, chitinase and glucanase.

In the context of the present invention, delta-endotoxins (e.g., cry1Ab, cry1Ac, cry1F, cry Fa2, cry2Ab, cry3A, cry Bb1 or Cry 9C) or vegetative insecticidal proteins (Vip) (e.g., vip1, vip2, vip3 or Vip 3A) are understood to obviously also include mixed toxins, truncated toxins and modified toxins. Hybrid toxins are recombinantly produced by a new combination of different domains of those proteins (see, e.g., WO 02/15701). Truncated toxins, such as truncated Cry1 abs, are known. In the case of modified toxins, one or more amino acids of the naturally occurring toxin are replaced. In such amino acid substitutions, it is preferred to insert non-naturally occurring protease recognition sequences into the toxin, such as, for example, in the case of Cry3A055, cathepsin-G-recognition sequences into the Cry3A toxin (see WO 03/018810).

Examples of such toxins or transgenic plants capable of synthesizing such toxins are disclosed, for example, in EP-A-0 374 753, WO 93/07278, WO 95/34656, EP-A-0 427 529, EP-A-451 878 and WO 03/052073.

Methods for preparing such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above. CryI-type deoxyribonucleic acids and their preparation are known, for example, from WO 95/34656, EP-A-0 367 474, EP-A-0 401 979 and WO 90/13651.

Toxins included in transgenic plants render the plants tolerant to harmful insects. Such insects may be present in any insect taxa but are particularly common in beetles (Coleoptera), diptera (Diptera), and moths (Lepidoptera).

Transgenic plants comprising 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 YIELDGARD (maize variety, expressed Cry1Ab toxin), YIELDGARD ROOTWORM (maize variety, expressed Cry3Bb1 toxin), YIELDGARD PLUS (maize variety, expressed Cry1Ab and Cry3Bb1 toxin), starlink (maize variety, expressed Cry9C toxin), herculex I (maize variety, expressed Cry1Fa2 toxin and enzyme phosphinothricin N-acetyltransferase (PAT) that acquires tolerance to herbicide phosphinothricin), nuCOTN B (cotton variety, expressed Cry1Ac toxin), bollgard I (cotton variety, expressed Cry1Ac toxin), bollgard II (cotton variety, expressed Cry1Ac and Cry2Ab toxin), vipCot (cotton variety, expressed Vip3A and Cry1Ab toxin), newLeaf (potato variety, expressed Cry3A toxin), natureGard, agrisure (GA 21) and Bt 3B (Bt) resistance to glyphosate, and Bt 3 CB (Protecta) are maize with the properties of maize.

Further examples of such transgenic crops are:

bt11 maize from seed company of Fangzhi (SYNGENTA SEEDS SAS), huo Bite (CHEMIN DE L' Hobit) 27, F-31 790 san Su Weier (St. Sauveur), france accession number C/FR/96/05/10. Genetically modified maize is rendered resistant to attack by european corn borer (corn borer and cnaphalocrocis medinalis) by transgenic expression of truncated Cry1Ab toxins. Bt11 maize also transgenically expresses PAT enzyme to obtain tolerance to the herbicide glufosinate ammonium.

Bt176 corn from seed of Fangda, huo Bite way 27, F-31 790 san Su Weier, france accession number C/FR/96/05/10. Genetically modified maize, genetically expressed as a Cry1Ab toxin, is resistant to attack by european corn borers (corn borers and cnaphalocrocis medinalis). Bt176 maize also transgenically expresses the enzyme PAT to obtain tolerance to the herbicide glufosinate ammonium.

MIR604 corn from seed of first come, huo Bite, line 27, F-31 790 san Su Weier, france, accession number C/FR/96/05/10. Corn that has been rendered insect-resistant by transgenic expression of the modified Cry3A toxin. The toxin is Cry3A055 modified by insertion of a cathepsin-G-protease recognition sequence. The preparation of such transgenic maize plants is described in WO 03/018810.

MON 863 corn from Monsanto Europe S.A.), 270-272 Teflon (Avenue DE Tervuren), B-1150 Brussels, belgium, accession number C/DE/02/9.MON 863 expresses a Cry3Bb1 toxin and is resistant to certain coleopteran insects.

IPC 531 cotton from Mengshan European company, 270-272 Teflon, B-1150 Brussels, belgium, accession number C/ES/96/02.

6.1507 Maize from pioneer overseas company (Pioneer Overseas Corporation), tedelsco, avenue Tedesco, 7B-1160 Brussell, belgium, accession number C/NL/00/10. Genetically modified corn, expresses the protein Cry1F to obtain resistance to certain lepidopteran insects, and expresses the PAT protein to obtain tolerance to herbicide grass Dingan.

NK603×MON 810 maize from Mengshan European company 270-272 Teflon, B-1150 Brussels, belgium under accession number C/GB/02/M3/03. By crossing the genetically modified varieties NK603 and MON 810, it is made up of a conventionally bred hybrid maize variety. NK603×MON 810 maize transgenes expressed the protein CP4 EPSPS obtained from Agrobacterium sp strain CP4 (made tolerant to the herbicide Roundup (containing glyphosate)), and also Cry1Ab toxins obtained from Bacillus thuringiensis subspecies (Bacillus thuringiensis subsp. Kurstaki) (made tolerant to certain lepidopteran insects, including European corn borer).

Additionally, no cross-resistance has been observed to date between a composition comprising a mixture of components (A) and (B) and any fungicidal solution for controlling phytopathogenic fungi such as Absidia, alternaria species, thiomyces species, cellularomyces species, aspergillus species (including Aspergillus flavus, aspergillus fumigatus, aspergillus nidulans, aspergillus niger, aspergillus terreus), aureobasidium species (including Aureobasidium pullulans), rhizopus dermatitis, blumeria brucei, bremia lactucae, staphylococcus species (including Vitis vinifera, vitis vinifera), vitis species (including Botrytis cinerea), cycloria species, cycloacae, Candida species (including candida albicans, candida glabrata, candida krusei, candida viticola, candida glabrata, candida tropicalis), cephaloascus fragrans, coralloides species, cercospora species (including brown spot germ), breviscaphis, cladosporium species, ergot, pachycoccobra, spira species, anthrax species (including colletotheca), cryptococcus neoformans, sedentary species, hyposporidium species, hypogaea species, elcospora species, epidermophyton species, piroxic species, colletotrichum species, and colletotrichum species, Powdery mildew species (including powdery mildew of Compositae), curvularia vitis, fusarium species (including Fusarium xanthophyllum, fusarium graminearum, F. Langsethiae, fusarium moniliforme, fusarium oxysporum, fusarium layering, fusarium subformum, fusarium solani), fusarium graminearum, gibberella fumosorosa, pachyrhizus, amomum melitensis, leptosphaera, bacillus bivalirus, byezoensis, leptosphaera species, alternaria species, histoplasma species (including histoplasma capsulatum), monascus turfgrass, leptographium lindbergi, leveillula taurica, confucius disturbs, rhizoctonia species, mucor species, cryptosporidium species (including Botrytis cinerea, leptosphaeria mali), basidiomycetes cacao, line mouth shells (Ophiostoma piceae), paracosporium species, penicillium species (including Penicillium digitatum, penicillium, pitrichum species, peronospora species (including Peronospora zeae. Fr, philippine and Peronospora miltiorrhizae), peronospora species, rhizoctonia solani, phellinus species, phoma pseudobulb, phoma grape, phoma pseudobulb, phytophthora species (including potato late blight), plasmodium species (including sunflower downy mildew, grape downy mildew), grifola species, fomitopsis species (including Saccharum gracilis, rhizoctonia cerealis, pseudomonas fragi, pseudomonas species (including Pseudomonas aeruginosa, humulus scandens), pseudodish-tube-bundle species, puccinia species (including Rhizoctonia cerealis, puccinia recondita, rhizoctonia cerealis, wheat leaf rust), sclerotinia species, nuclear species, pyricularia species (including Pyricularia oryzae), pythium species (including Pythium gracile), pythium species, rhizoctonia species, rhizomucor parvulus, rhizopus arrhizus, corallospora species, podophyllum species (including cercospora spinosa and s. prolificans), leptosphaeria, sclerotinia species, sclerotium species, septoria species (including septoria nodorum, septoria tritici), alternaria, septoria punctata (mono-ascus), sporotrichum species, septoria nodorum, phoma stolonifer species, hard leather fungus, cupola, rhizoctonia solani, tiepia species, trichoderma species (including trichoderma harzianum, trichoderma pseudokoningii, trichoderma viride), trichoderma species, sclerotium species, trichoderma species, and the like, The grape hook shell, the smut species, the black powder species the genus Sphaeromyces species (including Alternaria apple), verticillium species, and Xanthomonas species, in particular the number of the elements to be processed, the plant species may be selected from the group consisting of conidiophore, puccinia recondita, puccinia strigosa, gramichthora graminis, leptosphaeria, trichum taurinum, tricornutum, alternaria solani, alternaria alternata, alternaria feiji, alternaria cucumeris, alternaria meloidogyna, alternaria pisifera, verticillium dahliae, rhizoctonia cerealis, rhizoctonia solani, leptosphaera colchicis, botrytis cinerea, sclerotinia sclerotiorum, alternaria lunata, clostridium Xuehuimum and Alternaria malis.

In fact, fungicidal resistant strains of any of the species as outlined above have been reported in the scientific literature, wherein the strain resistant to one or more fungicides is from at least one of the following fungicidal mode of action classes, an extracellular quinone inhibitor (QoI), an intracellular quinone inhibitor (QiI), a succinate dehydrogenase inhibitor (SDHI) and a sterol demethylation inhibitor (DMI). Such fungicidal resistant strains may contain:

A mutation in the mitochondrial cytochrome b gene that confers resistance to a Qo inhibitor, wherein the mutation is G143A, F L or G137R. See, for example, gisi et al, PEST MANAG Sci [ Pest management science ] 2000, 56, 833-841, lucas, pestic Outlook [ pesticide prospect ] 2003, 14 (6), 268-70, fraaije et al, phytopathol [ Plant pathology ] 2005, 95 (8), 933-41, sierotzki et al, pest Manag, sci [ Pest management science ] 2007, 63 (3), 225-233 (2007), semar et al, J.plant Dis. Prot. [ Plant disease and protection journal ] 2007, (3), 117-119, and Pasche et al, J.crop protection journal ] 2008, 27 (3-5), 427-435 (2008).

A mutation in the mitochondrial cytochrome b gene that confers resistance to a Qi inhibitor, wherein the mutation is G37A/C/D/S/V or N31K. See, e.g., meunier et al, PEST MANAG SCI [ pest management science ] 2019, 75:2107-2114, young et al, PEST MANAG SCI [ pest management science ] 2018, 74 (2): 489-498, walker et al, environ, microbiol [ environmental microbiology ] 2021 (https:// doi.org/10.1111/1462-2920.15760.)

A mutation in a gene encoding a SdhB, C, D subunit that confers resistance to an SDHI inhibitor, wherein the mutation is in the following major pathogen:

Botrytis cinerea B-P225H/L/T/Y/F, B-N230I, B-H272L/Y/R, C-P80H/L, C-N87S;

Alternaria solani is B-H278R/Y, C-H134R/Q, D-D123E, D-H133R and C-H134R;

Septoria aethiopica, sdhB, N225T, N, 225I, R, 265, P, T, 268, I, T, 268A. In sdhC, T79N, T79I, W80S, W80A, A F, N86S, N86A, P127A, R M/S/T/G, R151S, R T, H R/Y, V166M, T R. In sdhD, I50F, M114V, D129G, T p+k186R;

the Rhizoctonia cerealis (Pyrenophora teres) is S66P, N, 235I, H Y277 in sdhB. In sdhC, K49E, R64K, N75S, G79R, H134R, S R. In sdhD, D124E, H134R, G138V, D145G;

Mortierella sepedonioides (Ramularia collo-cygni) in sdhB N224T, T267I. In sdhC, N87S, G91R, H R/L, G171D, H153R;

the phakopsora pachyrhizus (Phakopsora pachyrhizi) is C-I86F;

Sclerotinia sclerotiorum (Sclerotinia sclerotiorum) H273Y in sdhB. In sdhC, G91R, H R is used. In sdhD, T108K, H132,132, 132R, G150R.

The main sources of information are www.frac.info, sierotzki and Scalliet, phytopathology [ Plant pathology ] (2013) 103 (9): 880-887 and Sim õ es et al, j.plant dis.prot. [ journal of Plant disease and protection ] 2018, 125:21-2.

Mutations or combinations of mutations in the CYP51 gene conferring resistance to DMI inhibitors, wherein these mutations are L50S, D134G, V A/C, Y137F, S188N, A G, I381V, deletions 459-460, Y461H/S, N513K, S T. The primary sources of information are www.frac.info, cools et al, plant Pathol [ Plant pathology ] 2013, 62:36-42 and Schmitz HK et al, pest Manag. Sci [ Pest management science ] 2014, 70:378-388.

Thus, in a preferred embodiment, the composition according to the invention comprising a mixture of components (A) and (B) is used to control fungal strains that are resistant to one or more fungicides from any of the following fungicidal MoA classes, an extra-quinone inhibitor (QoI), an intra-quinone inhibitor (QiI), a succinate dehydrogenase inhibitor (SDHI) and a sterol demethylation inhibitor (DMI).

The compositions of the present invention, including all of the above disclosed embodiments and preferred examples thereof, may be mixed with one or more additional pesticides, including additional fungicides, insecticides, nematicides, bactericides, acaricides, growth regulators, chemosterilants, semiochemicals, insect repellents, attractants, pheromones, feeding stimulants or other bioactive compounds to form a multi-component pesticide giving a broader spectrum of agricultural protection.

Examples of such agricultural protectants and compositions of the invention may be formulated as:

Fungicides, such as trifluralin, fluazinam, benalaxyl-M (gealaxyl), furalaxyl, metalaxyl-M (metalaxyl-M), doxazosin, N ' - (2, 5-dimethyl-4-phenoxy-phenyl) -N-ethyl-N-methyl-formamidine, N ' - [4- (4, 5-dichloro-thiazol-2-yloxy) -2, 5-dimethyl-phenyl ] -N-ethyl-N-methyl-formamidine, N ' - [4- [ [3- [ (4-chlorophenyl) methyl ] -1,2, 4-thiadiazol-5-yl ] oxy ] -2, 5-dimethyl-phenyl ] -N-ethyl-N-methyl-formamidine, Ethaboxam, 3' -chloro-2-methoxy-N- [ (3 RS) -tetrahydro-2-oxofuran-3-yl ] acetyl-2 ',6' -dimethylaniline (imazalil), cyprodinil, pyrimethanil, dithianon, aureomycin, blasticidin-S, diphenyl, difenoconazole, chlornitramine, benzovindiflupyr, fluxazoxamide, hexachlorobenzene, pentachloronitrobenzene, tetraethoxynitrobenzene (TCNB), tolclofos, metrafenone, 2, 6-dichloro-N- (4-trifluoromethyl benzyl) -benzamide, fluopicolide (fluopicolide), thiocyanobenzamide, sulfenamide, benomyl, carbendazim hydrochloride, chlorbendazole, mequindox, thiabendazole, thiophanate-methyl, benthiavalicarb-amine, chlormebendazole, thiabendazole, alac-type benzene, chlorothalonil, benzalkonium, benomyl (IKF-309), alac-type benzene-S-methyl, piroxicam (KIF-7767), butylamine, 3-iodo-2-propynyl N-butylcarbamate (IPBC), tetrazolium, polyurethane, propamocarb, trifluoracene, 3- (difluoromethyl) -N- (7-fluoro-1, 3-tetramethyl-indan-4-yl) -1-methyl-pyrazole-4-carboxamide, dicyclopentadienyl, N- [ (5-chloro-2-isopropyl-phenyl) methyl ] -N-cyclopropyl-3- (difluoromethyl) -5-fluoro-1-methyl-pyrazole-4-carboxamide, N-cyclopropyl-3- (difluoromethyl) -5-fluoro-N- [ (2-isopropylphenyl) methyl ] -1-methyl-pyrazole-4-carboxamide, cyclopropylamide, chlorothalonil, flumorph, hydroxyquinoline copper, cymoxanil, fluorothiazole nitrile, thiazopyr-nitrile, ethiprole, iprodione, procymidone, ethephon, bupirimate, O-enemie, nitrofen, miticide, dimetoram, mitidol, diphenylamine, clomiphos, 2, 6-dimethyl- [1,4] dithiazide [2,3-c:5,6-c' ] bipyrrolidinyl-1, 3,5,7 (2H, 6H) -tetraketone, thiram oxide, Thiozin, thiram, mancozeb, wilford, metiram (metiram, polyram), zineb, mancozeb, methyl zineb, celen, wilford (wilford sodium), zineb, ziram, disulfide, ipratropium, ethaboxam, ethylphosphonic acid, fosetyl-aluminum (fosetyl-aluminum), methyl bromide, methyl iodide, methyl isothiocyanate, cycloxaprine, formamide, validamycin, streptomycin, (2 RS) -2-bromo-2- (bromomethyl) glutaronitrile (bromothalonil), dodine, doxifugine, biguanide octyl salt, biguanide octyl amine triacetate, 2,4-D, 2,4-DB, Kasugamycin, methiodin, cycloxaprid, hymexazol, hydroxyisoxaflutole, imazalil sulfate, oximidazole, fenoxanil, prochloraz, triflumizole, imidazolone, polado mixture, calcium polysulfide, copper acetate, copper carbonate, copper hydroxide, copper naphthenate, copper oleate, copper king, copper hydroxyquinoline, copper silicate, copper sulfate, copper fatty acid copper, cuprous oxide, sulfur, carbaryl, phthalide (clobazate), ding Jun (triazodone), flumethazine, zofurben, mandipropamid, KSF-1002, benzasection Mo Fu, dimethomorph, fenpropimorph, tridemorph, molbenomyl, diethofencarb, triphenyltin acetate, triphenyltin hydroxide, carboxin, dixyl, famoxadone, m-phenylphenol, p-phenylphenol, tribromophenol (TBP), 2- [2- [ (7, 8-difluoro-2-methyl-3-quinolinyl) oxy ] -6-fluoro-phenyl ] propan-2-ol 2- [ 2-fluoro-6- [ (8-fluoro-2-methyl-3-quinolinyl) oxy ] phenyl ] propan-2-ol, cyflufenamid, furalamid, oxadixyl, flufenamid, mefenamid, iprovalicarb, fenpiclonil, fludioxonil, pencycuron, fenoxanil, dimoxystrobin, phosphorous acid, folpet, captan, triazophos, fenpropidin, pink-making agent, osthole, 1-methylcyclopropene, 4-CPA, chlormequat chloride, bendazac acid, 2, 4-D-propionic acid (dichlorprop), desmothioate, oxadiazon, ethephon, flumetralin, gibberellic acid, gibberellin, hymexazol, maleic hydrazide, mepiquat chloride, naphthylacetamide, paclobutrazol, propiophenone, calcium propiophenone, thidiazuron, des She Lin (tributyl trithiophosphate), trinexapac, uniconazole, alpha-naphthylacetic acid, polyoxin D (polyoxin D, polyoxrim), BLAD, chitosan, fenoxanil, folpet, 3- (difluoromethyl) -N-methoxy-1-methyl-N- [ 1-methyl-2- (2, 4, 6-trichlorophenyl) ethyl ] pyrazole-4-carboxamide, Bixafen, fluxapyroxad, furametpyr, isopyrazam, penflufen, penthiopyrad, epoxiconamine, fenpyraclostrobin, pyridaben, pyripyroxime, boscalid, fluopicolide, fluoxastrobin, chloropyrimidol, 5-fluoro-2- (p-tolylmethoxy) pyrimidin-4-amine azoxystrobin, dimethachlon (dimetadone), fluquindone, iodoquinazolinone, somatostatin, quinoxyfen, 4, 5-trifluoro-3, 3-dimethyl-1- (3-quinolinyl) isoquinoline, 4-difluoro-3, 3-dimethyl-1- (3-quinolinyl) isoquinoline, 5-fluoro-3, 4-tetramethyl-1- (3-quinolinyl) isoquinoline, 9-fluoro-2, 2-dimethyl-5- (3-quinolinyl) -3H-1, 4-benzoxazepine, iso-Ding Yiyang-quinoline, oxolinic acid, fenamic acid (hydroxythioquinolone (oxythioquinox), quinoxymesylate (quinoxymethionate)), spiroxamine, (E) -N-methyl-2- [2- (2, 5-dimethylphenoxymethyl) phenyl ] -2-methoxy-iminoacetamide, azoxystrobin, coumoxystrobin, dimoxystrobin, enoxystrobin, enoxastrobin, fenamidate, flufenamate, fluoxastrobin, kresoxim-methyl, tolfenpyrad, Carbamate, phenoxymycylamine, trifloxystrobin, picoxystrobin, pyraclostrobin, chloromycetin, trifloxystrobin, indazole sulfenamid, dichlofluanid, tolylfluanid, but-3-ynyl N- [6- [ [ (Z) - [ (1-methyltetrazol-5-yl) -phenyl-methylene ] amino ] oxymethyl ] -2-pyridinyl ] carbamate, dazomet, isothiabendazole, thiabendazole, benzothiostrobin (TCC), silthiopham, zoxamide, dichlormid, tricyclazole, (rac) -cis-1- (4-chlorophenyl) -2- (1H-1, 2, 4-triazol-1-yl) -cycloheptanol (cyproconazole), 1- (5-bromo-2-pyridinyl) -2- (2, 4-difluorophenyl) -1, 1-difluoro-3- (1, 2, 4-triazol-1-yl) propan-2-ol 2- (1-tert-butyl) -1- (2-chlorophenyl) -3- (1, 2, 4-triazol-1-yl) -propan-2-ol (TCDP), azaconazole, bitertanol (bitertanol), furfuryl azole, climbazole, cyproconazole, difenoconazole, dimetazole, diniconazole-M, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriazole, hexaconazole, imibenconazole, ipconazole, isofluconazole, metconazole, Myclobutanil, penconazole, propiconazole, prothioconazole, simeconazole, tebuconazole, fluoroether oxazole, triazolone, triadimenol, imidazole, triticonazole, haloxyfop-methyl-5- [ (4-fluorophenyl) methyl ] -1-hydroxy-2, 2-dimethyl-cyclopentyl ] methyl ] -4H-1,2, 4-triazole-3-thione, 2- [ [3- (2-chlorophenyl) -2- (2, 4-difluorophenyl) oxiran-2-yl ] methyl ] -4H-1,2, 4-triazole-3-thione, flumetsulam (imidium), iprovalicarb, valicarb, 2-benzyl-4-chlorophenol (chlorophenol), Allyl alcohol, carfentrazone, benzalkonium chloride, chloropicrin, cresol, danazol Cisse (daracide), dichlorophenol (myclobutanil), difenoconazole, pyrithione, N- (2-p-chlorobenzoylethyl) -hexachloride lead, NNF-0721, xin Saitong, cyclosulfamuron, propamidine, and propionic acid.

Insecticides such as avermectin, acephate, acetamiprid, sulfametofen (S-1955), avermectin, azadirachtin, methyl thiotepa, bifenthrin, bifenazate, buprofezin, carbofuran (carbofuran), bardan, chlorantraniliprole (DPX-E2Y 45), chlorfenapyr, chlorpyrifos, methyl chlorpyrifos, chromafenozide, clothianidin, cyflumetofen, cyhalothrin, beta-cyhalothrin cyhalothrin, lambda-cyhalothrin, cyromazine, deltamethrin, diafenthiuron, diazinon, dieldrin, diflubenzuron, tetramethrin, dimethoate, dinotefuran, cyhalothrin, deltamethrin, and the like benomyl, emamectin, endosulfan, fenvalerate, ethiprole, benfocarb, fenoxycarb, fenpropathrin, fenvalerate, fipronil, flonicamid, flubendiamide fenvalerate, tau-fluvalinate, pyrimethanil (UR-50701), flufenoxuron, dinotefuran, chlorfenozide, hexaflumuron, triaflumuron, imidacloprid, indoxacarb, iso Liu Lin, lufenuron, chlorpyrifos, chlorfenapyr, chlorpyrifos, chlorfenapyr, and chlorpyrifos malathion, metaflumizone, metaldehyde, methamidophos, methidathion, methoprene, monocrotophos, methoxyfenozide, nitenpyram Nitroethylurea thiazole, bisphenylfluorourea, polyfluourea (XDE-007), methomyl, parathion, methyl parathion, permethrin, phorate, phoxim, fosetyl, triazamate, profenofos, praziquantel, pymetrozine, acetamiprid, pyrethrin, pyridalyl, flubenflumorph, pyrazolopyridine (pyriprole), pyriproxyfen, rotenone, rimexodine, spinetoram, spinosad, spirodiclofen, spiromesifen (BSN 2060), spirotetramat, fenpropiphos, tebufenozide, flubenuron, tefluthrin, terbutafos, chlorfenapyr, thiacloprid, thiamethoxam, thiodicarb, dimefon, tetrabromothrin, triazamate, trichlorfon and chlorfenapyr;

bactericides such as streptomycin;

Acaricides such as amitraz, fenamic, ethylacet acaricidal cyenopyrafen, tricyclotin, chlorfenapyr, chlorpyrifos, chlorfenapyr, chlor etoxazole, fenazaquin, fenbutatin oxide, fenpropathrin, fenpyroximate, hexythiazox, propargite, pyridaben and tebufenpyrad; and

Biological agents such as bacillus thuringiensis, bacillus thuringiensis delta endotoxins, baculoviruses and entomopathogenic bacteria, viruses and fungi.

Other examples of "reference" mixture compositions are as follows (wherein the term "TX" denotes a compound (definition of component (A) of the composition according to the invention) selected from a compound having formula (I), or a compound having formula (I-A), or selected from (X.01), (X.02), (X.03), (X.04), (X.05), (X.06), (X.07), (X.08), (X.9), (X.10), a compound having formula (I-A), Or (X.11), as defined in Table X above, selected from the group consisting of (4E, 10Z) -tetradec-4, 10-dienylacetate+TX, (7E, 9Z) -dodeca-7, 9-dien-1-ylacetate+TX, (E) -6-methylhept-2-en-4-ol+TX, (E) -dec-5-en-1-ylacetate and (E) -dec-5-en-1-ol+TX, (E) -tridec-4-en-1-ylacetate+TX, (S) -bioallyl-7-en-1-ylacetate+TX, (Z) -hexadec-11-enal+TX, (Z) -hexadec-13-en-11-yn-1-ylacetate+TX, (Z) -eicos-13-en-10-one+TX, (Z) -tetradec-1-yl-4-ylacetate+TX, (Z) -hexadec-7-en-1-yl-1-ylacetate+TX, (Z) -hexadec-11-ylacetate+TX monoacetate+TX, 1-bis (4-chlorophenyl) -2-ethoxyethanol+TX, 1- (2-chlorophenyl) -3, 3-dimethyl-2- (1, 2, 4-triazol-1-ylmethyl) butan-2-ol+TX, 1- (5-bromo-2-pyridinyl) -2- (2, 4-difluorophenyl) -1, 1-difluoro-3- (1, 2, 4-triazol-1-yl) propan-2-ol+TX, 1-hydroxy-1H-pyridine-2-thione+TX, 1-methylcyclopropene+TX, 1-naphtyl-acetamide+TX, 1-naphthylacetic acid+TX, 2-dichloroethylene-2-ethylsulfinylethyl methyl-phosphate+TX, 2, 4-D+TX, 2, 4-DB+TX, 2, 6-dichloro-N- (4-trifluoromethylbenzyl) benzamide+TX, 2- (1, 3-dithio-2-yl) phenyldimethyl-carbamate+2- (2, 4-dichloro-N- (4-trifluoromethylbenzyl) propan-2-ol+TX, 2-hydroxy-1H-pyridine-2-thione+TX, 1-methylcyclo-yl) 2- (2, 2-ethy-ethoxymethyl) 2- (2, 4-ethy-propylmethyl) carbamate+TX, 2-ethy-ethoxymethyl-ethyl-phosphonate+TX, 2, 4-D+TX, 2-dichloro-2-methyl-ethyl-2-yl-methyl-alcohol+TX -3-carboxamide + TX, 2- (octylthio) ethanol + TX, 2-bromo-2-bromomethyl-glutaronitrile + TX, 2-chlorovinyldiethyl phosphate + TX, 2-imidazolidinone + TX, 2-methyl (prop-2-ynyl) aminophenylmethylcarbamate + TX, 2-cyanothioethyl laurate + TX, 3- (4-chlorophenyl) -5-methylrhodamine + TX, 3- (difluoromethyl) -1-methyl-N- [1, 3-trimethylindan-4-yl ] pyrazole-4-carboxamide + TX, 3- (difluoromethyl) -N- (7-fluoro-1, 3-tetramethyl-indan-4-yl) -1-methyl-pyrazole-4-carboxamide + TX, 3-chloro-6-methyl-4-phenylmethyl-4-carboxamide + TX, 3- (difluoromethyl) -1, 3-tetramethyl-indan-4-carboxamide + TX, 3-trifluoromethyl-4-carboxamide + TX, 3- (difluoromethyl) -N- (7-fluoro-1, 3-tetramethyl-indan-4-carboxamide + TX - (2, 6-difluorophenyl) -6-methyl-5-phenyl-pyridazin-3-carbonitrile +TX, 4- (2-bromo-4-fluoro-phenyl) -N- (2-chloro-6-fluoro-phenyl) -2, 5-dimethyl-pyrazol-3-amine +TX, 4- (quinoxalin-2-ylamino) benzenesulfonamide +TX, 4- [ [6- [2- (2, 4-difluorophenyl) -1, 1-difluoro-2-hydroxy-3- (1, 2, 4-triazol-1-yl) propyl ] -3-pyridinyl ] oxy ] benzonitrile +TX, 4-chloro-2- (2-chloro-2-methyl-propyl) -5- [ (6-iodo-3-pyridinyl) methoxy ] pyridazin-3-one +TX, 4-CPA +TX, 4-methyl (prop-2-ynyl) amino-3, 5-xylylmethylcarbamate +TX, 4-methylnon-5-ol and 4-methylnon-5-one +TX, 4-phenyl-2-hydroxy-3- (1, 2, 4-difluoro-1-pyridinyl) propyl ] -3-pyridinyl ] benzonitrile +TX, 4-chloro-2- (2-methyl-propyl) -5- [ (6-iodo-3-pyridinyl) methoxy ] pyridazin-3-one +TX, 4-CPA +TX, 4-methyl-2-methyl-N-yl-amine +TX Base+tx; 5-fluoro-2- (p-tolylmethoxy) pyrimidin-4-amine +TX, 5-hydroxy-6-methyl-4- (((E) -pyridin-3-ylmethylene) amino) -4, 5-dihydro-1, 2, 4-triazin-3 (2H) -one +TX, 5-methyl-6-thio-1, 3, 5-thiadiazin-3-ylacetic acid +TX, 8-hydroxyquinoline sulfate +TX, 11-ethyl-10, 12-dioxo-2, 5, 8-trite-4, 11-diazatricyclo [7.3.0.03,7] dodeca-1 (9), 3, 6-triene-6-methylnitrile +TX, 14-methyl octadeca-1-ene +TX, [ (9Z, 11E) -tetradec-9, 11-dienyl ] acetate +TX, [ (Z) -dodeca-9-enyl ] acetate +TX, abamectin +TX, acephate +TX, chlorfenamide +TX, chlor +TX, 11-ethyl-10, 12-dioxo-2, 11-diaza-n +TX, 11-trioxaprop-1 +TX, 3-E +TX, 14-methyl octadeca-1-alkene +TX, TX-n +TX-n-methyl-1 +TX, TX-dioptric acid +TX-n-N-methyl-n +TX-n-N-E +N-methyl-n +E + Ecdysone+tx; alpha-pleocidin+TX, amblyseius species. +TX; ametoctradin+tx; fruit racing + TX; the composition comprises the components of fenpyroximate+TX, chlorfenpyrad+TX, triazophos+TX, amifostine+TX, apium, primum, anthraquinone+TX, antranium, short-range aphid+TX, cotton parasitic bee+TX, aphid+TX, ethylmethidat+TX, golden system mycin+TX, alfalfa silver moth+NPV+TX, abametin (1 a) +TX, azaconazole+TX, azamethine A+TX, azamethide+TX, methylpiperon+TX, ethylgua+TX, methyl valley phosphorus+TX, pyrimidol+TX, sphaerin+TX, spherical bacillus+TX, antranium, primum, bazachlor+TX, bazafium+TX, bazafium, bazaum, bah, bah+TX, bajijijijijijijibs, bah, bajijijijin, bajin, ban, babajin, ban, bababajin-bap-bajin-Cyin-Cyfabacjibababababababababababababababajibs- -; benzothiazine+tx; bifenazate+tx; bifenthrin+tx; de-mite+TX, biopesthrin+TX, pencythrin+TX, biochanin+TX, dexfenpropidin+TX, bicinchonne+TX, bicifluron+TX, bitriazole+TX, bipyramid+TX, cinerea+TX, borax+TX, bodder-mixing agent+TX, boscalid+TX, bromacil+TX, ethylbromacil+TX, furacil+TX, toxazin+TX, bupiridone+TX, buserelin +TX, busulfan+TX, but-3-alkynyl N- [6 ] [ (1-methyltetrazole-5-yl) -phenyl-methylene ] amino ] methyl ] -2-pyridinyl ] carbamate+TX, stock-removing, terbuzin+TX, terbuzinone+TX, decadone+TX, decamethrin+TX, benone+TX, buproflumin+TX, buprofezin+TX, bupirin+TX +TX; carbosulfan+tx; carboxin+tx; carprofen + TX, cyclopropylamide + TX, cartap-hydrochloride + TX, cephalexin + TX, ceftizoxime + TX, ceftiofur + TX, cestex + TX, veratrine + TX, methoxam + TX, chitosan + TX, methoxam + TX, chloralose + TX, chlorantranin + TX, chloralfos-TX, TX-chloralfosin-TX, TX-sepmomex + TX, TX-chlorin-TX, TX-sepin-TX, TX-sepin-TX, TX-Tx, TX-Tx, and, TX-Tx, TTTTTTx, TTTTTTTTTTTTTTTTTTTTTTTTTTTTTTTTTTTTTTTTTTTTTTTTTTTTTTTTTTTTTTTand, +TX, copper acetate+TX, copper hydroxide+TX, copper naphthenate+TX, copper octoate+TX, copper oleate+TX, copper oxide+TX, copper oxychloride+TX, copper silicate+TX, copper sulfate+TX, copper (II) +TX, chlorpropham+TX, warfarin+TX, mouse killer+TX, methyl ester (jiaxiangjunzhi) +TX, phosphorus livestock+TX, coumarone+TX, cryolite+TX, cryptolepidium monnieri+TX, melon fly sex attractant+TX, thiabendazole bactericide+TX, cuprous oxide (I) +TX, benzonitrile phosphine+TX, phosphorus fruit+TX; cyazofamid+tx; cyclobutyronitrile+TX; cyprodinil + TX; cyantranin+TX, cyclo Ding Fulun +TX, malus pomonella GV+TX, cyclopyralid+TX, cyclofluanide+TX, cyflumetofen+TX, cyhalothrin+TX, fenphos+TX, cyhalothrin+TX, cypermethrin (cis-cypermethrin) +TX, fencythrin+TX, cyproconazole+TX, cyprodinil+TX, cyromazine+TX, cytokinin+TX, dextrorotathrin+TX, siberian ion-Px+TX, DAEP +TX, cotton-n+TX, DCPM+TX, prochloraz+TX, demethyl-Pv+TX, bromofenhexan+TX, telephos-O+TX, inner suction phosphorus-S-methyl+TX, suction phosphorus+TX, butyl phosphorus+TX, cyprodin+TX, cimetin+N, N-methyl-N, N TX; diethofencarb+tx; the mosquito repellent amine + TX; the composition comprises the following components of (1) tricks, difenoconazole, delphinidin, timonazole, flufenzine, chlorpyrifos, fluoxastrobin, trichloraz, pea fumet, she Yingji, infertility, tetramethrin, trichloraz, dimemamectin, dimethachlon, timberine, methrin, methodol, dimethomorph, dimethicone, dimethyl disulfide, dimethyl phthalate, dichlorvos, dimetryn, dichlorvos, diniaposin, dinium, dinotebufenide, TX, dinotefuran, spinosamine, dithiazole, oxamide, spinosad, tetramethrin, decamethrin, and (1-tetramethrin; straw+tx; toxic phosphorus + TX; enestroburin (enoxastrobin) +tx; enrofloxacin + TX, entomopathogenic bacteria + TX, entomopathogenic fungi + TX, entomopathogenic viruses + TX, EPBP + TX, epoxiconazole + TX, irinotecan + TX, stock horn aphid + TX, fenvalerate + TX, epoxiconazole + TX, ethaboxam + TX, folpet + TX, ethiprole + TX, ethionine + TX, YITIP + TX, methiphos + TX, longline + TX, 4-methyl octanoate + TX, ethyl formate + TX, ethylhexanediol + TX, epprin + TX, etoxazole + TX, hymexazol + TX, ethionine + TX, eugenol + TX, crotamiton + TX, EXD + TX, tip end lure + TX, oxazolone + TX, fanisol + TX, feban (febantel) + TX, imidazolone + TX, methidating + TX, fenpropinquamide + TX Seed +TX; topiramate+tx; cyhalothrin+TX; fenpropathrin+tx, fenpropidin+tx, fenpropimorph+tx, fenpropidone+tx, fenpyroximate+tx, nematodos+tx, phoxim+tx, ethylphoxim+tx, triphenyltin+tx, triphenyltin acetate+tx, triphenyltin chloride+tx, triphenyltin hydroxide+tx, fenvalerate+tx, fern (ferbam) +tx, azomethizone+tx, iron phosphate+tx, fipronil+tx, fipronil bisamide+tx, fipronil+tx; flucyclox+tx; flucycloxuron + TX; flucycloxuron + TX; flufenthrinate, fludioxonil, flucythrinate, flufenamid, azoxystrobin, flufenoxuron, flufenuron, flufenphos, trifloxystrobin, TX, fluindenonamide, flubutamid, trifloxystrobin, TX, flumorph, flupyrimid, flutebufenpyr, fluxapyroxazin, fluoxapirtine, fluazoxystrobin, fluflufluquinconazole, tebufenphos, fluflufluquinconazole, flupyrifos, flusilazole, sulfenpyr, fluthiazolazen, fluamid, flutx, flufenhexamid, fluvalicamid, fluvalinate, chlorpyrifos, TX, formaldehyde, valicamid, TX, chlorfenpyr, trichloretum, trioxaprop, melamine, chlorfenpyr, flufenpyr, flufenphos, flufenmid, flufenphos, flufenmid, fluvalinate, flucycloxaprop, fluxaprop, tip, fluxaprop-X, and, fluxaprop-X, tip, fluxaprop-X, and, which are in-up, and the composition of the composition is Heptylphosphine+tx; 2, the bacteria heterodera and heterodera+TX; hexaconazole+tx; hexadecyl cyclopropanecarboxylate+tx, hexaflumuron+tx, hexidine+tx, thiamethoxam+tx, catchment+tx, cycloxapride (rac- (1 s,2 s) -1- (4-chlorophenyl) -2- (1, 2, 4-triazol-1-yl) cycloheptyl) +tx, flumetsulane+tx, hydrated lime (calcium hydroxide) +tx, hymexazol+tx, hexaflumetsula+tx, elcatin+tx, clothing Ma Ning (hypericin) +tx, imazalil+tx, amidazole+tx, imidacloprid+tx, biguanide+tx, indoxacarb+tx, indenopyraz+tx, iodopropynyl butylcarbamate+tx, iprovaliconazole+tx, valicamid+tx, valicarb+tx, iprovaliconazole+tx, iprovalicon; jasmine II+TX; juvenile hormone i+tx; juvenile hormone ii+tx; young hormone III+TX, thienyl, kanamycin+TX, kasugamycin+TX, kasugamycin hydrochloride hydrate+TX, kinetin+TX, nitenpyram+TX, kresoxim-methyl, kulark (kurstaki) +TX, lambda-cyhalothrin+TX, clobetan-methyl, brombenfop+TX, levamisole+TX, trimethyl tricyclononane+TX, propyrium+TX, powder-vein sex attractant+TX, lufenuron+TX, ribbonic, ricketxin (lvbenmixianan) +TX, thiazolephos+TX, mesityl methyl carbamate+TX, dark black spiny, magnesium phosphide+TX, marathon+TX, propisocyan+TX, cabbage, NPV+TX, copper-methyl, zinc-methyl, tx, deran+TX, manganese-methyl, deram+TX, tricyclin+TX, chlorfenpyr-methyl, fluben-methyl, cycloxaprop-methyl, and methyl, respectively, etc +TX; wibprop-Potassium+TX; the preparation method comprises the following steps of (1) mu-sodium+TX, (Huang Kuobing) pallet+TX, (yellow green muscardine fungus+TX, (scara green muscardine fungus) microsporose variety+TX, (pyridine oxamide+TX, (leaf fungus+TX, (carbofuran+TX), (methamidophos+TX), (thiodicarb+TX), (methidathion+TX), (methiocarb+TX), (butenaminphos+TX, (methoprene+TX), methoprene+TX, (methyl pyrethrin+TX), methoxyfenozide+TX, (methyl oxazine+TX), sequorin+TX, (methyl iodide+TX), (methyl neodecanoamide+TX, (ambroxb+TX), methidatumerin+TX, (methidatume+TX), oxamide+TX, (oxadone+TX), phenone+TX, (tetrazodone+TX), speed-phosphorus+TX; Mgk264+tx; milbemycins) +tx; milbeoxime+tx; indocarpium [5- (2-isopropylphenyl) methyl ] -1-methyl-pyrazole-4-carboxamide, N-cyclopropyl-3- (difluoromethyl) -5-fluoro-N- [ (2-isopropylphenyl) methyl ] -1-methyl-pyrazole-4-carboxamide, sodium-substituted-for-TX, dibromophosphorus-substituted-TX, NC-170-substituted-TX, nemulin-substituted-TX, nitrosin-substituted-N- [2, 4-dichloro-phenoxy ] phenyl ] -3- (difluoromethyl) -1-methyl-pyrazole-4-carboxamide, N-cyclopropyl-3- (difluoromethyl) -5-fluoro-4-carboxamide, N-cyclopropyl-5-nitro-4-substituted-N- (2-isopropyl) -substituted-4-nitro-4-carboxamide, nitrosin-substituted-N-nitro-4-carboxamide, nitrosin-substituted-nitro-amine-N, nitrosin-substituted-nitro-amine-4-carboxamide, nitrosin-nitro-amine-substituted-amine-substituted-N, nitrosin-nitro-amine-base-amine, and dye-base-amine-base, o' -tetrapropyl disulfide substituted pyrophosphate+tx; octadeca-2, 13-dien-1-ylacetate + TX; octadeca-2, 13-dien-1-ylacetate + TX; xin Saitong +TX, furalamide+TX, oleic acid+TX, omethoate+TX, olympic acid+TX, origanum species+TX, oryzanol+TX, osthole+TX, nicotine+TX, fenoxicam+TX, oxadixyl+TX, oxamide+TX, oxabendazole+TX, oxybenzone+TX, oxine+TX, oxolinic acid+TX, oxaimidazole+TX, oxabushing+TX, pefurin+TX, foenicillin+TX, isosulfor+TX, foenicillin+TX, terramycin+TX, doxorubin+TX, mesoxycillin+TX, p-oxon+TX, parathion+TX, pabenazol+TX, penoxsulam+TX, pentazophos+TX, oxamide+TX, oxadol+TX, methiphos+TX, methione+TX, pyrithione+TX, P+TX, P-thiamine+TX The phosphocarb and TX; phosphonic acid+tx; phosphorus+tx; phoxim, methyl phoxim, four-corkton, chile small phytoseite, piprazole, picoxystrobin, pimobendan, porzite, polycarbamate, porzite, potassium-N-ethyl xanthogen, potassium-hydroxyquinoline, potassium-sulfate, praziquante, prazite, proczite, profenophos, porzite, and, porzite, porin, porzite, and gliclain, porin, P, porin, P, and, P, and +TX; pyraclostrobin+tx; pidinafop-propargyl+TX; bipyramid+TX, fixed phosphorus+TX, pyrazolo (pyrazoxone) +TX, antichlorethamine+TX, pyrethrin I+TX, pyrethrin II+TX, pyrethrin (natural product) +TX, pyrethroid (natural product) +TX, pyribenzoxim+TX, pyridaben+TX, flubenamazine+TX, pyridalyl+TX, pyridaben-4-amine+TX, pyripyroxime+TX, praziquantel+TX, pyrimethanil+TX, pyriminox+TX, pyriminobac+TX, pyriminodone+TX, pyripyroxim+TX, pyriminoxidil+TX, fluquindox+TX, fluquintoxyl+TX, quinalphos-methyl+TX, chloranil+TX, quinolone-melin+TX, quinine+TX, fluvalinomide+TX, livestock phosphorus+TX; Quindox+tx; pentachloronitrobenzene+tx; R-1492+TX; R-metalaxyl+TX, giant knotweed extract+TX, ribavirin+TX, rotenone+TX, rimidine (ryanodine+TX, sabatron+TX, octamethyl-phosphorus+TX, sea onion glycoside+TX, octreomine+TX, flumetralin+TX, selametin+TX, synergistic chrysanthemum+TX, sesamolin+TX, tricyclo+TX, silafluofen+TX, thiasilamine+TX, silicon fluazole+TX, sodium tetrathiocarbonate+TX, sulon+TX, banana bulb trunk attractant+TX, spinetoram+TX, spirotetramine+TX Mao Wen nematode+TX, small volume nematode+TX, night light nematode+TX, brio nematode (STEINERNEMA RIOBRAVE) +TX, lycrate+TX, tsujuga+TX, 5, 7, 5, 62, 24, 34, 48 and 35, 48, TX, and 35, TX +TX; butyl pyrimidine phosphorus + TX; tetraoxynitrobenzene+tx; fluofluben-3, tefluthrin-3, dithian-3, cycloprothrin-3, tertbutyloxy-Tx-3, tertbutyloxy-3, tx-3, tx-34, tx-3, tx-Tx, T trichlormetaphos) -3+ TX; toxic soil phosphine+TX; trichogramma species + TX; triclopyr (triclabendazole) +TX, chloromycetin, tricyclozole+TX, pinocyclic bacteria+TX, snail+TX, trifloxystrobin+TX, triflumizole+TX, triflumuron+TX, oxazine+TX, mediterranean fly attractant+TX, mediterranean fly attractant A+TX, mediterranean fly attractant B1+TX, mediterranean sea fly attractant B2+TX, mediterran sea fly attractant C+TX, triclopyr+TX, triomycin+TX, trinitrotoluene+TX, trinexanthema+TX, trinexanthema-ethyl+TX, nitenpyram+TX, mycetin+TX, mycetin+TX, truinc-call+TX, tolramycin+TX, cilobroman+TX, uniconazole+TX, udre+TX, udre+TX, umbet+TX, VALIFENALATE +TX, aphiduo+TX vaniliprole +TX, dine+TX, base+Tx+TX, pyveroni+TX, trinitrotoluene+TX, PYZ+3-CHO+XMexiconazole+TX, CHO+TX, CHO+XMexiconazole+TX, CHO+XYZ+3-CHO+XMexiconazole+TX, CHO+XYZ+XYZ+3, CHO+CHO+CHO+CHO+XYR+CHO+CHO+CHO+XO+CHO+CHO+CHO+CHO+CHO+CHO+CHO+CHO+CHO+CHO+CHO+CHO+CHO 3-carboxamide (this compound can be prepared by the method described in WO 2014/095675) +tx, methyl 3- [ (4-chlorophenyl) methyl ] -2-hydroxy-1-methyl-2- (1, 2, 4-triazol-1-ylmethyl) cyclopentanecarboxylate (this compound can be prepared by the method described in WO 2019/093522) +tx, (2R) -methyl 2- [ 2-chloro-4- (4-chlorophenoxy) phenyl ] -2-hydroxy-3- (1, 2, 4-triazol-1-yl) propionate (this compound can be prepared by the method described in WO 2019/093522) +tx; 5- [5- (difluoromethyl) -1,3, 4-oxadiazol-2-yl ] -N- [1- (2, 6-difluorophenyl) cyclopropyl ] pyrimidin-2-amine (this compound can be prepared by the method described in WO 2021/255093) +TX; aminopyrafen (this compound can be prepared by the method described in WO 2014/006945) +TX; dipivoxine (this compound can be prepared by the method described in WO 2011/138281) +TX; 1- [6- (difluoromethyl) -5-methyl-3-pyridinyl ] -4, 4-difluoro-3, 3-dimethyl-isoquinoline (this compound can be prepared by the method described in WO 2017/016915) +TX; 1- [4- (difluoromethoxy) -2-methyl-phenyl ] -2- (1, 2, 4-triazol-1-yl) -1- [1- (trifluoromethyl) cyclopropyl ] ethanol (this compound can be prepared by the method described in WO 2021/249800) +1- [6- (difluoromethyl) -5-methyl-3-pyridinyl ] -4, 4-difluoro-3, 3-dimethyl-isoquinoline (this compound can be prepared by the method described in WO 2017/016915) +TX; 1- [4- (difluoromethoxy) -2-methyl-phenyl ] -2- (trifluoromethyl) cyclopropyl ] ethanol (this compound can be prepared by the method described in WO 2011/249800 ) -4, 4-difluoro-3, 3-dimethyl-isoquinoline (this compound can be prepared by the method described in WO 2017/016915) +tx, N-methyl-4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenylthiocarboxamide (this compound can be prepared by the method described in WO 2015/185485) +tx, 2-difluoro-N-methyl-2- [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] acetamide (this compound can be prepared by the method described in WO 2017/178245) +tx, trifluoracexazole+tx, N-methyl-4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] benzamide (this compound can be prepared by the method described in WO 2015/185485) +tx, (Z, 2E) -5- [1- (2, 4-dichlorophenyl) pyrazol-3-yl ] oxy-2-methoxy-pentylene-3-yl ] acetamide (this compound can be prepared by the method described in WO 2017/178245) +tx, N-methyl-4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] benzamide (this compound can be prepared by the method described in WO 2015/185485) +tx, 3-dimethyl-pent-3-enamine (this compound can be prepared by the method described in WO 2013/092224) +tx; methyl (2E) -2-methoxyimino-2- [ 3-methyl-2- [ [ (E) -1- [4- (trifluoromethyl) -2-pyridinyl ] ethyleneamino ] oxymethyl ] phenyl ] acetate (this compound can be prepared by the method described in WO 2022/033906) +TX, (2E) -2-methoxyimino-N-methyl-2- [ 3-methyl-2- [ [ (E) -1- [4- (trifluoromethyl) -2-pyridinyl ] ethyleneamino ] oxymethyl ] phenyl ] acetamide (this compound can be prepared by the method described in WO 2022/033906) +TX, (2E) -2- [2- [ (E) - [3- (4-fluorophenyl) -1-methyl-prop-2-ynyl ] amino ] oxymethyl ] -3-methyl-phenyl ] -2-methoxyimino-N-methyl-acetamide (this compound can be prepared by the method described in WO 1/249928) +TX, (2E) -2- [2- [ (E) -3- (4-fluorophenyl) -1- [ -prop-2-ynyl ] amino ] oxymethyl ] -3-methyl-acetamide Methyl 2-alkynylene ] amino ] oxymethyl ] -3-methyl-phenyl ] -2-methoxyimino-acetate (this compound may be prepared by the method described in WO 2021/249928) +tx 3- [2- (1-chlorocyclopropyl) -3- (3-chloro-2-fluoro-phenyl) -2-hydroxy-propyl ] imidazole-4-carbonitrile (this compound may be prepared by the method described in WO 2016/156290) +tx 3- [2- (1-chlorocyclopropyl) -3- (2-fluoro-phenyl) -2-hydroxy-propyl ] imidazole-4-carbonitrile (this compound may be prepared by the method described in WO 2016/156290) +tx 2- [6- (4-bromophenoxy) -2- (trifluoromethyl) -3-pyridinyl ] -1- (1, 2, 4-triazol-1-yl) propan-2-ol (this compound may be prepared by the method described in WO 2017/029179) +tx; 2- [6- (4-chlorophenoxy) -2- (2-hydroxy-propyl) imidazole-4-carbonitrile (this compound may be prepared by the method described in WO 2016/156290) +tx 2- [6- (4-bromophenoxy) -2- (trifluoromethyl) -3-pyridinyl ] -1- (1, 2, 4-triazol-1-yl) propan-2-ol (this compound may be prepared by the method described in WO 2017/029179) (difluoromethyl) -1,3, 4-oxadiazol-2-yl ] -N- [1- (2-fluorophenyl) ethyl ] pyrimidin-2-amine (this compound may be prepared by the method described in WO 2021/255093) +tx, 5- [5- (difluoromethyl) -1,3, 4-oxadiazol-2-yl ] -N- [1- (3, 5-difluorophenyl) ethyl ] pyrimidin-2-amine (this compound may be prepared by the method described in WO 2021/255093) +tx, N- [1- (2-fluorophenyl) cyclopropyl ] -5- [5- (trifluoromethyl) -1,3, 4-oxadiazol-2-yl ] pyrimidin-2-amine (this compound may be prepared by the method described in WO 2021/255093) +tx, 5- [5- (difluoromethyl) -1,3, 4-oxadiazol-2-yl ] -N- [1- (2, 6-difluorophenyl) ethyl ] pyrimidin-2-amine (this compound may be prepared by the method described in WO 2021/255093) +tx; 2- (difluoromethyl) -5- [2- [1- (2, 6-difluorophenyl) cyclopropyloxy ] pyrimidin-5-yl ] -1,3, 4-oxadiazole (this compound may be prepared by the method described in WO 2021/255093) +tx, 5- [5- (difluoromethyl) -1,3, 4-oxadiazol-2-yl ] -N- [1- (2-fluorophenyl) cyclopropyl ] pyrimidin-2-amine (this compound may be prepared by the method described in WO 2021/255093) +tx, 5- [ (4-bromo-2-methyl-phenyl) methyl ] -3- [3- (3-chloro-2-fluoro-phenoxy) -6-methyl-pyridazin-4-yl ] -5, 6-dihydro-4H-1, 2, 4-oxadiazine (this compound may be prepared by the method described in WO 2021/255070) +tx, 3- [3- (3-cyclopropyl-2-fluoro-phenoxy) -6-methyl-pyridazin-2-yl ] -5- [ (3-bromo-2-methyl-phenyl) methyl ] -3- [3- (3-chloro-2-fluoro-phenoxy) -6-methyl-pyridazin-4-yl ] -5, 6-dihydro-4H-1, 2, 4-oxadiazine (this compound may be prepared by the method described in WO 2021/255070) +tx, 3- [3- (3-cyclopropyl-2-fluoro-phenoxy) -6-methyl-pyridazin-4-yl ] -5- [ -2-amino Phenyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] oxazole-4-carboxamide ethyl ester (which may be prepared by the methods described in WO 2022/133114) +TX, ethyl 1- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenoxy ] methyl ] pyrazole-4-carboxylate (which may be prepared by the methods described in WO 2022/133114) +TX, ethyl 1- [ [4- [ (Z) -2-ethoxy-3, 3-trifluoro-prop-1-yloxy ] phenyl ] methyl ] pyrazole-4-carboxylate (which may be prepared by the methods described in WO 2020/056090 and WO 2021/183707) +TX, ethyl 1- [ [4- [ [2- (trifluoromethyl) -1, 3-dioxolan-2-yl ] methoxy ] phenyl ] methyl ] pyrazole-4-carboxylate (which may be prepared by the methods described in WO 2022/056090 and WO 2021/133114) +ethyl 1- [ [4- [ (Z) -2-ethoxy-3, 3-trifluoro-prop-1-eny ] phenyl ] methyl ] pyrazole-4-carboxylate (which may be prepared by the methods described in WO 2020/056090 and WO 2021/183707) +TX- [4- [ [2- (trifluoromethyl) -1- [ [2- (2-dioxolan-2-yl ] methoxy ] phenyl ] methyl ] pyrazole-4-carboxylate (which may be prepared by the methods described in WO 2020/3/p-yl ] phenyl ] methyl ] carboxylate Methyl-2-methyl-phenyl-methyl-carbamate (this compound may be prepared by the method described in WO 2020/097012) +tx; methyl N- [ [5- [1- (4-cyclopropyl-2, 6-difluoro-phenyl) pyrazol-3-yl ] -2-methyl-phenyl ] methyl ] carbamate (this compound can be prepared by the method described in WO 2020/097012) +TX; methyl 2- [ 2-chloro-4- (4-chlorophenoxy) phenyl ] -2-hydroxy-3- (1, 2, 4-triazol-1-yl) propionate (this compound can be prepared by the method described in WO 2019/093522) +TX; 4, 5-trifluoro-3, 3-dimethyl-1- (3-quinolinyl) isoquinoline+TX; 5-fluoro-3, 4-tetramethyl-1- (3-quinolinyl) isoquinoline+TX; 2-methoxy-N- [ methoxy- [5- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] -2-thienyl ] methyl ] acetamide (this compound can be prepared by the method described in WO 2020/2513) +N- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] -2-thienyl ] methyl ] acetamide -methyl-propionamide (which may be prepared by the method described in WO 2020/256113) +TX; N- [ methoxy- [5- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] -2-thienyl ] methyl ] butyramide (which may be prepared by the method described in WO 2020/256113) +TX; 2- (difluoromethyl) -N- [ (3R) -3-ethyl-1, 1-dimethyl-indan-4-yl ] pyridine-3-carboxamide (which may be prepared by the method described in WO 2014/095675) +TX; 2- (difluoromethyl) -N- (3-ethyl-1, 1-dimethyl-indan-4-yl) pyridine-3-carboxamide (which may be prepared by the method described in WO 2014/095675) +TX; 2- (difluoromethyl) -N- (1, 3-trimethylindan-4-yl) pyridine-3-carboxamide+TX; 2- (difluoromethyl) -3- [ 3-chloro-4-yl) pyridine-3-carboxamide (which may be prepared by the method described in WO 2014/095675) +TX; 2- (difluoromethyl) -N- (1, 3-trimethylindan-4-yl) pyridine-3-carboxamide (which may be prepared by the method described in WO 2014/095675), (2- (3-ethyl-indan-4-yl) pyridine-3-carboxamide (which may be prepared by the method described in WO 2014/095675) Preparation of) +TX (5S) -3- [3- (3-chloro-2-fluoro-phenoxy) -6-methyl-pyridazin-4-yl ] -5- [ (2-chloro-4-methyl-phenyl) methyl ] -5, 6-dihydro-4H-1, 2, 4-oxadiazine (this compound may be prepared by the methods described in WO 2020/127780, WO 2021/255070) +TX (3- [3- (3-chloro-2-fluoro-phenoxy) -6-methyl-pyridazin-4-yl ] -5- [ (2-chloro-4-methyl-phenyl) methyl ] -5, 6-dihydro-4H-1, 2, 4-oxadiazine (this compound may be prepared by the methods described in WO 2020/127780), Preparation of (Z) -3-methoxy-2- (2-methyl-5-phenyl-phenoxy) prop-2-enoic acid methyl ester (this compound can be prepared by the method described in JP 2023078251) +TX; 2- [ (2, 6-difluoro-4-pyridinyl) - (2-methylpropanoyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide +TX; or its (R) or (S) enantiomer or mixture +TX (this compound can be prepared by the method described in WO 2017207362 A1), WO 2019105933 A1, WO 2020109511 A1, WO 2021244952 A1), 2- [ (2, 6-difluoro-4-pyridinyl) - (tetrahydropyran-4-carbonyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide + TX, or its (R) or (S) enantiomer or mixture + TX (this compound may be prepared from WO 2017207362 A1, WO 2019105933 A1, WO 2020109511 A1), Prepared by the method described in WO 2021244952 A1), 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -5-methyl-N-spiro [3.4] oct-3-yl-thiazole-4-carboxamide +TX, or its (R) or (S) enantiomer or mixture +TX (this compound may be prepared by the method described in WO 2017207362 A1, WO 2019105933 A1, WO 2020109509 A1), 2- [ cyano- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide +TX, or its (R) or (S) enantiomer or mixture +TX (this compound may be prepared by the method described in WO 2017207362 A1, WO 2019105933 A1, WO 2020109509 A1), 2- [ (2, 6-difluoro-4-pyridinyl) - (2-methoxyacetyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide + TX, or its (R) or (S) enantiomer or mixture + TX (this compound may be prepared by the method described in WO 2017207362 A1, WO 2019105933 A1, WO 2020109511 A1, WO 2021244952 A1), 2- [ acetyl- (2, 6-difluoro-4-pyridinyl) amino ] -5-methyl-N-spiro [3.4] oct-3-yl-thiazole-4-carboxamide + TX, or its (R) or (S) enantiomer or mixture + TX (this compound may be prepared by the method described in WO 2017207362 A1, WO 2021244952 A1), WO 2019105933 A1, WO 2020109511 A1, N-methoxy-N- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] cyclopropanecarboxamide (which may be prepared by the method described in WO 2017/055473) +TX, (Z) -2- (5-cyclopentyl-2-methyl-phenoxy) -3-methoxy-prop-2-enoic acid methyl ester (which may be prepared by the method described in WO 2020/193387) +TX, (Z) -2- (5-cyclohexyl-2-methyl-phenoxy) -3-methoxy-prop-2-enoic acid methyl ester (which may be prepared by the method described in WO 2020/193387) +TX; N- [ (1R) -1-benzyl-1, 3-dimethylbutyl ] -8-fluoroquinoline-3-carboxamide (which may be prepared by the method described in WO 2017/380) +TX; N- [ (1S) -1-benzyl-1, 3-dimethylbutyl ] -8-fluoroquinoline-3-carboxamide (which may be prepared by the method described in WO 2020/193387) +n- [ (1537) -2-fluoro-pyridines-3-carboxamide) - (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide +TX, or its (R) or (S) enantiomer or mixture +TX (this compound may be obtained from WO 2017207362 A1), Prepared by the method described in WO 2019105933 A1, WO 2020109511 A1, WO 2021244952 A1 2- [ acetyl- (2, 6-difluoro-4-pyridinyl) amino ] -N- (2, 2-dimethylcyclobutyl) -5-methyl-thiazole-4-carboxamide +TX, or its (R) or (S) enantiomer or mixture +TX (this compound can be obtained from WO 2017207362 A1, WO 2019105933 A1, WO 2020109511 A1), Prepared by the method described in WO 2021244952 A1), N, 2-dimethoxy-N- [ [4- [5- (trifluoromethyl) -1,2, 4-oxadiazol-3-yl ] phenyl ] methyl ] -propionamide + TX, or the (R) or (S) enantiomer or mixture thereof + TX (this compound may be prepared by the method described in WO 2017/055473).

The reference in brackets after the active ingredient, for example [3878-19-1], refers to the chemical abstract accession number. The above described mixed formulations are known. In the case where the active ingredients are included in "THE PESTICIDE Manual [ handbook of pesticides ]" [ THE PESTICIDE Manual-A World Compendium handbook of pesticides-global overview ]; 13 th edition, edit: C.D.S. TomLin; the British Crop Protection Council [ England crop protection Committee ] ], they are described therein with the entry numbers given in parentheses above for the particular compound, for example, the compound "avermectin" is described with the entry number (1). In the case where "[ CCN ]" is added to a specific compound above, the compound in question is included in "Compendium of Pesticide Common Names [ pesticide common name schema ]" which is available on the Internet [ A. Wood; compendium of Pesticide Common Names, copyright @ 1995-2004], for example, the compound "Acetylfipronil" is described in the Internet address http:// www.alanwood.net/pesticides/acetope

Most of the active ingredients described above are indicated by the so-called "common name" hereinabove, the corresponding "ISO common name" or another "common name" being used in different situations. In case the name is not a "common name", the name category used is replaced by the name given in parentheses for the specific compound, in which case IUPAC name, IUPAC/chemical abstract name, "chemical name", "conventional name", "compound name" or "development code" is used, or "alias" is used if neither one of those names nor "common name" is used. "CAS registry number" means a chemical abstract registry number.

The term "compound of formula (I)" refers to component a.

In the "reference" mixture composition, the compound of formula (I) (selected from the compounds of formula (I), (I-A), or from (X.01), (X.02), (X.03), (X.04), (X.05), (X.06), (X.07), (X.08), (X.9), (X.10), or (X.11), as listed in (above) Table X) and the mixture of active ingredients described above comprises a compound selected from Table X (above) and an active ingredient as described above, which is preferably in a mixing ratio from 100:1 to 1:100, especially from 50:1 to 1:50, more especially from 20:1 to 1:20, even more especially from 10:1 to 1:10, very especially from 5:1 to 1:5, especially preferably from 2:1 to 1:2, and the ratio from 4:1 to 1:1 is also preferably from 1:5:1, or 5:1, 3, 3:3, 3:4:3, 3:2 or 4:3:3, 3:3 or 4:3:3, 3:2 or 4:3:3:3 or 4:3:2, 3:3 or 4:3:3 or 4:2:1:2, or 4:1:1:10, very especially from 5:1:1:1:1:1) Or 1:600, or 1:300, or 1:150, or 1:35, or 2:35, or 4:35, or 1:75, or 2:75, or 4:75, or 1:6000, or 1:3000, or 1:1500, or 1:350, or 2:350, or 4:350, or 1:750, or 2:750, or 4:750. Those mixing ratios are by weight.

These mixed compositions as described above (both according to the invention and "reference" mixed compositions) can be used in a method of controlling pests, which method comprises applying a composition comprising a mixture as described above to the pest or its environment.

Mixtures comprising a compound of formula (I) (selected from compounds of formula (I), or compounds of formula (I-a), or selected from (x.01), (x.02), (x.03), (x.04), (x.05), (x.06), (x.07), (x.08), (x.9), (x.10), or (x.11), as listed in table X (above)) and one or more active ingredients as described above, may be applied, for example, as a single "ready-to-use" form, as a combined spray mixture (which mixture consists of separate formulations of single active ingredient components, such as a "tank mix"), and as such, when applied in a sequential manner (i.e. one after another for a moderately short period of time, such as hours or days). The order of administration of these compounds of formula (I) selected from table X (above) and these active ingredients as described above is not critical to the practice of the invention.

The compositions of the invention may also be used for crop enhancement. According to the invention, 'crop enhancement' means an improvement in plant vigor, an improvement in plant quality, an improved tolerance to stress factors and/or an improved input utilization efficiency.

According to the invention, 'improvement of plant vigour' means that certain traits are improved in quality or quantity when compared with the same traits of a control plant that has been grown under the same conditions but not using the method of the invention. Such traits include, but are not limited to, early and/or improved germination, improved emergence, ability to use fewer seeds, increased root growth, more developed root system, increased root nodulation, increased bud growth, increased tillering, stronger tillers, more efficient tillers, increased or improved plant stand, fewer plant inversions (PLANT VERSE) (lodging), increase and/or improvement in plant height, increase in plant weight (fresh weight or dry weight), larger leaves, greener leaf color, increased pigment content, increased photosynthetic activity, earlier flowering, longer panicles, early grain maturity, increased seed, fruit or pod size, increased number of pods or ears, increased seed number per pod or ear, increased seed quality, enhanced seed filling, fewer dead basal leaves, delayed wilting, improved plant vigour, increased amino compound levels in stored tissues and/or less fertilizer (e.g., less needed, less fertilizer and/or less water input) and/or labor. Plants with improved vigour may have an increase in any of the above traits or any combination or two or more of the above traits.

According to the invention, 'improvement of plant quality' means that certain traits are improved in quality or quantity when compared with the same traits of control plants that have been grown under the same conditions but have not used the method of the invention. Such traits include, but are not limited to, improved plant visual appearance, reduced ethylene (reduced production and/or inhibition of reception), improved quality of harvested material (e.g., seeds, fruits, leaves, vegetables) (such improved quality may manifest as improved visual appearance of harvested material), improved carbohydrate content (e.g., increased sugar and/or starch content, improved sugar acid ratio, reduced sugar, increased sugar formation rate), improved protein content, improved oil content and composition, improved nutritional value, reduced anti-nutritional compounds, improved organoleptic properties (e.g., improved taste) and/or improved consumer health benefits (e.g., increased vitamin and antioxidant levels), improved post-harvest characteristics (e.g., enhanced shelf life and/or storage stability, easier processability, easier compound extraction), more homogenous crop development (e.g., simultaneous germination, flowering and/or fruiting of plants) and/or improved seed quality (e.g., for use in subsequent seasons). Plants with improved quality may have an increase in any of the foregoing traits or any combination or two or more of the foregoing traits.

According to the invention, 'improved tolerance to stress factors' means that certain traits are improved in quality or quantity when compared with the same traits of control plants that have been grown under the same conditions but not using the method of the invention. Such traits include, but are not limited to, increased tolerance and/or resistance to a variety of abiotic stress factors that induce suboptimal growth conditions such as drought (e.g., any stress that results in a lack of water content, a lack of water absorption potential, or a decrease in water supply to the plant), chilling, heating, osmotic stress, UV stress, flooding, increased salinity (e.g., salinity in the soil), increased mineral exposure, ozone exposure, high light exposure, and/or limited nutrient (e.g., nitrogen and/or phosphorus nutrient) utilization. Plants with improved tolerance to stress factors may have an increase in any of the above traits or any combination or two or more of the above traits. In the case of drought and nutrient stress, these tolerance improvements may be due to, for example, higher efficiency of absorption, utilization or retention of water and nutrients.

According to the present invention, 'improved input utilization efficiency' means that plants can be grown more effectively using a given input level when compared to the growth of control plants grown under the same conditions but without the method of the present invention. In particular, these inputs include, but are not limited to, fertilizers (e.g., nitrogen, phosphorus, potassium, micronutrients), light, and water. Plants having improved input utilization efficiency may have improved use of any of the above inputs, or any combination of two or more of the above inputs.

Other crop enhancements of the invention include reduced plant height, or reduced tillering, which is a beneficial feature in crops or under conditions where less biomass and less tillering is desired.

Any or all of the above crop enhancements may result in improved yield by improving, for example, plant physiology, plant growth and development, and/or plant type. In the context of the present invention, 'yield' includes, but is not limited to, (i) an increase in biomass production, grain yield, starch content, oil content, and/or protein content, which may result from (a) an increase in the amount produced by the plant itself or (b) an improved ability to harvest plant material, (ii) a compositional improvement in the harvested material (e.g., improved sugar acid ratio, improved oil composition, increased nutritional value, reduction in anti-nutritional compounds, increased consumer health benefits), and/or (iii) an increased/facilitated ability to harvest the crop, improved crop processability, and/or better shelf stability/shelf life. Increased yield of an agricultural plant means that, where quantitative measures may be taken, the yield of a product of each plant is increased by a measurable amount over the yield of such same product produced by the plant under the same conditions (but without the application of the invention). According to the invention, it is preferred that the yield is increased by at least 0.5%, more preferably by at least 1%, even more preferably by at least 2%, still more preferably by at least 4%, preferably by 5% or even more.

Any or all of the above crop enhancements may also result in land utilization improvements, i.e., land that was previously unavailable or suboptimal for planting may become available. For example, plants that exhibit increased viability under drought conditions can be planted in suboptimal rainfall areas (e.g., likely at the edge of a desert or even in a desert).

In one aspect of the invention, crop enhancement is obtained in the substantial absence of stress from pests and/or diseases and/or abiotic stresses. In another aspect of the invention, improvements in plant vigor, stress tolerance, quality and/or yield are obtained in the substantial absence of stress from pests and/or diseases. For example, pests and/or diseases may be controlled by applying a pesticidal treatment prior to or simultaneously with the method of the invention. In yet another aspect of the invention, improvements in plant vigor, stress tolerance, quality and/or yield are obtained in the absence of pest and/or disease stress. In further embodiments, the improvement in plant vigor, quality and/or yield is obtained in the absence or substantial absence of abiotic stress.

The compositions of the present invention may also be used in the field of protecting stored goods from fungal attack. According to the invention, the term "stored goods" is understood to mean natural substances of vegetable and/or animal origin and their processed forms, which are taken from the natural life cycle and which are intended for long-term protection. Stored goods of plant origin, such as plants or parts thereof (e.g. stalks, leaves, tubers, seeds, fruits or grains) may be protected in a freshly harvested state or in processed form, such as pre-dried, moistened, crushed, ground or roasted. Also falling under the definition of stored goods are wood, whether in the form of raw wood, such as building timber, transmission towers and fences, or in the form of manufactured goods, such as furniture or objects made of wood. The stock goods of animal origin are hides, leather, fur, hair, etc. The composition according to the present invention can prevent adverse effects such as spoilage, discoloration or mold. Preferably, "stored goods" is understood to mean natural substances of vegetable origin and/or processed forms thereof, more preferably fruits and processed forms thereof (such as pomes, stone fruits, berries and citrus fruits and processed forms thereof). In another preferred embodiment of the invention, "stored goods" is understood to mean wood.

Accordingly, another aspect of the invention is a method of protecting stored goods, the method comprising applying a composition according to the invention to the stored goods.

The compositions of the invention can also be used in the field of protection of technical materials against fungal attack. According to the invention, the term "technical material" includes paper, carpeting, construction material, cooling and heating systems, wall panels, ventilation and air conditioning systems, etc., preferably "technical material" is understood to mean wall panels. The composition according to the present invention may prevent adverse effects such as spoilage, discoloration, or mold.

The compositions according to the invention are typically formulated in a variety of ways using formulation aids such as carriers, solvents and surface-active substances. The formulations may be in different physical forms, for example, in the form of dusting powders, gels, wettable powders, water-dispersible granules, water-dispersible tablets, effervescent compressed tablets, emulsifiable concentrates, microemulsifyable concentrates, oil-in-water emulsions, flowable oils, aqueous dispersions, oily dispersions, suspoemulsions, capsule suspensions, emulsifiable granules, soluble liquids, water-soluble concentrates (with water or water-miscible organic solvents as a carrier), impregnated polymeric films, or in other forms known, for example, from Manual on Development and Use of FAO and WHO Specifications for Pesticides [ handbook of development and use of FAO and WHO standards for pesticides ], united nations, first edition, second revision (2010). Such formulations may be used directly or may be diluted before use for reuse. Dilution may be performed with, for example, water, liquid fertilizer, micronutrients, biological organisms, oil or solvents.

These formulations can be prepared, for example, by mixing the active ingredient with formulation auxiliaries in order to obtain the compositions in the form of finely divided solids, granules, solutions, dispersions or emulsions. These active ingredients may also be formulated with other adjuvants such as finely divided solids, mineral oils, oils of vegetable or animal origin, modified oils of vegetable or animal origin, organic solvents, water, surface-active substances or combinations thereof.

These active ingredients may also be contained in microcapsules. The microcapsules contain the active ingredient in a porous carrier. This enables the active ingredient to be released (e.g., slowly released) into the environment in controlled amounts. The microcapsules typically have a diameter of from 0.1 to 500 microns. They contain the active ingredient in an amount of from about 25% to 95% by weight of the capsule. These active ingredients may be in the form of monolithic solids, in the form of fine particles in solid or liquid dispersants, or in the form of a suitable solution. The encapsulated film may comprise, for example, natural or synthetic rubber, cellulose, styrene/butadiene copolymers, polyacrylonitrile, polyacrylate, polyester, polyamide, polyurea, polyurethane or chemically modified polymer, or other polymers known to those skilled in the art. Alternatively, very fine microcapsules may be formed in which the active ingredient is contained in the form of finely divided particles in a solid matrix of the base substance, but these microcapsules are not themselves encapsulated.

Formulation auxiliaries suitable for preparing formulations according to the invention are known per se. As the liquid carrier, use may be made of: water, toluene, xylene, petroleum ether, vegetable oil, acetone, methyl ethyl ketone, cyclohexanone, anhydride, acetonitrile, acetophenone, amyl acetate, 2-butanone, butylene carbonate, chlorobenzene, cyclohexane, cyclohexanol, alkyl acetate, diacetone alcohol, 1, 2-dichloropropane, diethanolamine, p-diethylbenzene, diethylene glycol rosin acid ester, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, N, N-dimethylformamide, dimethyl sulfoxide, 1, 4-dioxane, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, diproxitol, alkylpyrrolidones, ethyl acetate, 2-ethylhexanol, ethylene carbonate, 1-trichloroethane, 2-heptanone, alpha-pinene, d-limonene, ethyl lactate, ethylene glycol butyl ether, ethylene glycol methyl ether, gamma-butyrolactone, glycerol acetate, glycerol diacetate, glycerol triacetate, hexadecane, hexylene glycol, isoamyl acetate, isobornyl acetate, isooctane, isophorone, ethylene glycol butyl ether isopropyl myristate, lactic acid, laurylamine, isopropylidene acetone, methoxypropanol, methyl isoamyl ketone, methyl isobutyl ketone, methyl laurate, methyl caprylate, methyl oleate, methylene chloride, m-xylene, N-hexane, N-octylamine, stearic acid, octylamine acetate, oleic acid, oleylamine, o-xylene, phenol, polyethylene glycol, propionic acid, propyl lactate, propylene carbonate, propylene glycol methyl ether, p-xylene, toluene, triethyl phosphate, triethylene glycol, xylene sulfonic acid, paraffin, mineral oil, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, propylene glycol methyl ether, diethylene glycol methyl ether, methanol, ethanol, isopropanol, and higher molecular weight alcohols such as amyl alcohol, tetrahydrofuranol, hexanol, octanol, ethylene glycol, propylene glycol, glycerol, N-methyl-2-pyrrolidone, and the like.

Suitable solid carriers are, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, diatomaceous earth, limestone, calcium carbonate, bentonite, calcium montmorillonite, cottonseed hulls, wheat flour, soybean flour, pumice, wood flour, ground walnut hulls, lignin, and the like.

Many surface-active substances can be advantageously used in both solid and liquid formulations, especially those formulations which can be diluted by a carrier before use. The surface-active substances may be anionic, cationic, nonionic or polymeric and they may be used as emulsifiers, wetting agents or suspending agents or for other purposes. Typical surface-active substances include, for example, salts of alkyl sulfates, such as diethanol ammonium lauryl sulfate, salts of alkylaryl sulfonates, such as calcium dodecylbenzene sulfonate, alkylphenol/alkylene oxide adducts, such as ethoxylated nonylphenol, alcohol/alkylene oxide adducts, such as ethoxylated tridecyl alcohol, soaps, such as sodium stearate, salts of alkyl naphthalene sulfonates, such as sodium dibutylnaphthalene sulfonate, salts of dialkyl sulfosuccinates, such as sodium di (2-ethylhexyl) sulfosuccinate, sorbitol esters, such as sorbitol oleate, quaternary amines, such as lauryl trimethyl ammonium chloride, polyethylene glycol esters of fatty acids, such as polyethylene glycol stearate, block copolymers of ethylene oxide and propylene oxide, and salts of monoalkyl phosphates and dialkyl esters, and also further substances, such as those described in McCutcheon' S DETERGENTS AND Emulsifiers Annual [ Makins cleaner and emulsifier annual ], MC company (MC Publishing Corp.), de, new Jersey (Ridgewood New Jersey) (1981).

Additional adjuvants that may be used in the pesticide formulation include crystallization inhibitors, viscosity modifiers, suspending agents, dyes, antioxidants, foaming agents, light absorbers, mixing aids, defoamers, complexing agents, substances and buffers that neutralize or alter the pH, corrosion inhibitors, fragrances, wetting agents, absorption enhancers, micronutrients, plasticizers, glidants, lubricants, dispersants, thickeners, anti-freezing agents, microbiocides, and liquid and solid fertilizers.

The formulation according to the invention may comprise additives comprising oils of vegetable or animal origin, mineral oils, alkyl esters of such oils or mixtures of such oils with oil derivatives. The amount of oil additive in the formulation according to the invention is generally from 0.01% to 10% based on the mixture to be applied. For example, the oil additive may be added to the spray can at the desired concentration after the spray mixture has been prepared. Preferred oil additives include mineral or vegetable-derived oils, such as rapeseed oil, olive oil or sunflower oil, emulsified vegetable oils, alkyl esters of vegetable-derived oils, such as methyl derivatives, or animal-derived oils, such as fish oil or tallow. Preferred oil additives include alkyl esters of C ₈-C₂₂ fatty acids, especially methyl derivatives of C ₁₂-C₁₈ fatty acids, such as methyl esters of lauric acid, palmitic acid, and oleic acid (methyl laurate, methyl palmitate, and methyl oleate, respectively). Many oil derivatives are known from Compendium of Herbicide Adjuvants [ herbicide adjuvant outline ], 10 th edition, university of south illinois, 2010.

These formulations generally comprise from 0.1 to 99% by weight, in particular from 0.1 to 95% by weight, of the compounds of component (a) and component (B) and from 1 to 99.9% by weight of a formulation auxiliary, preferably comprising from 0 to 25% by weight of a surface-active substance. Whereas commercial products may preferably be formulated as concentrates, the end user will typically use a diluted formulation.

The application rate varies within a wide range and depends on the nature of the soil, the application method, the crop plant, the pest to be controlled, the prevailing climatic conditions, and other factors dictated by the application method, the application time and the target crop. Generally, the composition or compound may be applied at a rate of from 1 to 2000 l/ha, especially from 10 to 1000 l/ha.

Certain mixture compositions comprising the compounds of formula (I) described above may show synergistic effects. This synergistic effect occurs whenever the effect of the combination of active ingredients is greater than the sum of the effects of the individual components. For a given combination of active ingredients, the expected effect E obeys the so-called COLBY (COLBY) formula and can be calculated as follows (COLBY, s.r. "Calculating SYNERGISTIC AND antagonistic responses of herbicide combination [ calculate synergistic and antagonistic response of herbicide combination ]".weeds [ weed ], volume 15, pages 20-22; 1967):

ppm = milligrams of active ingredient (=a.i.) per liter of spray mixture

X =% action on active ingredient a) using p ppm of active ingredient

Y =% action on active ingredient B) using q ppm of active ingredient.

The expected (additive) active ingredients a) +b) function, according to the cole ratio, using p+q ppm of active ingredient is:

If the actual observed effect (O) is greater than the expected effect (E), then the combined effect is superadditive, i.e., there is a synergistic effect. Mathematically, the synergy corresponds to a positive value of the difference of (O-E). In the case of purely complementary added actives (expected activity), the difference (O-E) is zero. Negative values of the difference (O-E) mark a loss of activity compared to the expected activity.

However, the compositions according to the invention may have further unexpectedly advantageous properties in addition to the actual synergistic effect with respect to fungicidal activity. Examples of such advantageous properties that may be mentioned are more favourable degradability, improved toxicological and/or ecotoxicological behaviour, or improved characteristics of the useful plants, including emergence, crop yield, more developed root system, increased tillering, increased plant height, larger leaves, fewer basal leaves death, stronger tillers, greener leaves colour, less fertilizer needed, less seeds needed, more tillers, earlier flowering, earlier grain maturation, less lodging (lodging) of the plants, enhanced shoot growth, improved plant vigor and early germination.

The composition according to the invention can be applied to phytopathogenic microorganisms, to useful plants, to the locus thereof, to propagation material thereof, to stored goods or to technical materials threatened by microbial attack.

The composition according to the invention can be applied before or after the useful plants, their propagation material, stored goods or technical material are infected with the microorganism.

The amount of the composition according to the invention to be applied will depend on various factors such as the compound used, the object of treatment, such as for example plants, soil or seeds, the type of treatment, such as for example spraying, dusting or seed dressing, the purpose of the treatment, such as for example prophylaxis or therapy, the type of fungus to be controlled or the time of application.

When applied to useful plants typically in combination with 1 to 5000 g a.i./ha, in particular 2 to 2000 g a.i./ha, for example, 100, 250, 500, 800, 1000, 1500 g a.i./ha, component (a) is typically applied at a rate of 5 to 2000 g a.i./ha, in particular 10 to 1000 g a.i./ha, for example, 50, 75, 100 or 200 g a.i./ha.

In agricultural practice, the application rate of the composition according to the invention depends on the type of action desired and is typically in the range from 20 to 4000 g total compositions per hectare.

When the composition according to the invention is used for treating seeds, it is generally sufficient to have a ratio of 0.001 to 50 g of the compound of component (A) per kg of seed, preferably from 0.01 to 10g per kg of seed, and 0.001 to 50 g of the compound of component (B) per kg of seed, preferably from 0.01 to 10g per kg of seed.

For the avoidance of doubt, where a literature reference, patent application, or patent is cited in the text of this application, the entire contents of said citation is incorporated herein by reference.

Examples

The following examples are intended to illustrate the invention and are not meant to limit the invention in any way.

The compounds of the invention may differ from the known compounds in greater efficacy at low application rates, as demonstrated by the skilled person using the experimental procedure outlined in the examples, using lower application rates (if necessary) such as 60 ppm, 20 ppm or 2 ppm.

The compounds having formula (I) may have a number of benefits, including in particular advantageous levels 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, advantageous activity profile, increased safety (including improved crop tolerance), improved physico-chemical properties, or increased biodegradability).

Throughout this specification, temperature is given in degrees celsius and "m.p." means melting point. LC/MS means liquid chromatography mass spectrometry, and the description of the apparatus and method is as follows.

¹ H NMR and ¹⁹ F NMR measurements were recorded on a Bruker 400MHz spectrometer, and chemical shifts were given in ppm relative to TMS (¹ H) and CFCl ₃（¹⁹ F standards. The spectra were measured in deuterated solvents as indicated. These compounds were characterized by any of the following LCMS methods. The characteristic LCMS values obtained for each compound are retention time ("Rt", recorded in minutes) and measured molecular ion (m+h) ⁺ or (M-H) ^-.

LC-MS method A spectra were recorded on a mass spectrometer (SQD, SQDII single quadrupole mass spectrometer) from Waters, equipped with an electrospray source (polarity: positive and negative ions, capillary: 3.00 kV, cone-hole range: 30V, extractor: 2.00V, source temperature: 150 ℃, desolvation temperature: 350 ℃, cone-hole gas flow: 50 l/h, desolvation gas flow: 650 l/h, mass range: 100 to 900 Da) and Acquity UPLC: binary pump, heated column chamber, diode array detector and ELSD detector from Waters. Waters UPLC HSS T3.8 μm,30 x 2.1 mm, temperature 60 ℃, DAD wavelength range (nm) 210 to 500, solvent gradient A=water+5% MeOH+0.05% HCOOH, B=acetonitrile+0.05% HCOOH, gradient 10% -100% B in 1.2 min, flow (ml/min) 0.85.

LC-MS method D spectra were recorded on a mass spectrometer (HPLC: UPLC 'H' grade) from the Acquiry QDA Mass spectrometer of Waters company equipped with an electrospray source (polarity: positive and negative ions (ionization method: electrospray (ESI), polarity: positive and negative polarity transitions), scanning type: full scan, capillary (kV): 0.8, cone voltage: 25.00V, source temperature: 120 ℃, desolvation gas flow: 1000L/Hr, desolvation temperature: 600 ℃, cone gas flow: 50L/Hr, mass range: 110 to 850 Da, PDA wavelength range: 230 to 400 nm).

Acquity UPLC HSS T3C 18 column, 30 mm column length, 2.1. 2.1 mm column inner diameter, 1.8 μ particle size, 40 column oven temperature

The chromatographic parameters are optimized with the gradient conditions of solvent a=water with 0.1% formic acid: acetonitrile 95:5 v/v, solvent b=acetonitrile with 0.05% formic acid

Examples of formulations

The combination is thoroughly mixed with these adjuvants and the mixture is thoroughly ground in a suitable mill, whereby a wettable powder is obtained which can be diluted with water to give a suspension of the desired concentration.

The combination is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable grinder, so that a powder is obtained which can be used directly for seed treatment.

Emulsifiable concentrate

Emulsions with any desired dilution that can be used in plant protection can be obtained from such concentrates by dilution with water.

The ready-to-use dust is obtained by mixing the combination with a carrier and grinding the mixture in a suitable grinder. Such powders may also be used for dry dressing of seeds.

Extruder pellets

The combination is mixed and ground with these adjuvants and the mixture is moistened with water. The mixture is extruded and then dried in an air stream.

Coated granules

This finely ground combination is applied uniformly in a mixer to kaolin wet with polyethylene glycol. In this way dust-free coated granules are obtained.

Suspension concentrate

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

Flowable concentrate for seed treatment

Sustained release capsule suspension

28 Parts of the combination are mixed with 2 parts of aromatic solvent and 7 parts of toluene diisocyanate/polymethylene-polyphenyl isocyanate-mixture (8:1). This mixture was emulsified in a mixture of 1.2 parts of polyvinyl alcohol, 0.05 parts of defoamer and 51.6 parts of water until the desired particle size was reached. To this emulsion was added 2.8 parts of a1, 6-hexamethylenediamine mixture in 5.3 parts of water. The mixture was stirred until the polymerization was completed. The capsule suspension obtained is stabilized by adding 0.25 parts of thickener and 3 parts of dispersant. The capsule suspension formulation contains 28% active ingredient. The diameter of the media capsule is 8-15 microns. The resulting formulation is applied to the seeds as an aqueous suspension suitable for use in the device for this purpose.

Formulation types include Emulsion Concentrates (EC), suspension Concentrates (SC), suspoemulsions (SE), capsule Suspensions (CS), water dispersible granules (WG), emulsifiable Granules (EG), emulsions, water-in-oil Emulsions (EO), oil-in-water Emulsions (EW), microemulsions (ME), oil Dispersions (OD), oil suspensions (OF), oil-soluble solutions (OL), soluble concentrates (SL), ultra-low volume Suspensions (SU), ultra-low volume solutions (UL), parent drugs (TK), dispersible Concentrates (DC), wettable Powders (WP), soluble Granules (SG) or any technically feasible formulation in combination with agriculturally acceptable adjuvants.

Abbreviations (abbreviations)

CDCl ₃ deuterated chloroform

DMF dimethylformamide

DMSO dimethyl sulfoxide

DMSO-d6 deuterated dimethyl sulfoxide

EtOAc ethyl acetate

HCl hydrochloric acid

H/hrs hours

LC-MS liquid chromatography mass spectrometry (LC-MS or LCMS)

Rh relative humidity

Rt room temperature

Rt retention time

Ssp subspecies

T3P propane phosphonic anhydride, also known as 2,4, 6-tripropyl-1,3,5,2,4,6-trioxatriphosphohexane-2, 4, 6-trioxide

THF tetrahydrofuran

Preparation example

The compounds of formula (I) according to the invention can be prepared using the synthetic techniques described above and below.

"Mp" refers to the melting point in degrees Celsius. The radicals represent methyl groups. ¹ H NMR and ¹⁹ F NMR measurements were recorded on a Bruker 400MHz spectrometer (or 600 MHz as indicated), chemical shifts are given in ppm relative to TMS (¹ H) and CFCl ₃（¹⁹ F standards. The spectra were measured in deuterated solvents as indicated. These compounds were characterized by any of the following LC-MS methods. The characteristic LCMS values obtained for each compound are retention time ("Rt", recorded in minutes) and measured molecular ion (m+h) ⁺ or (M-H) ^-.

The cis-isomer and trans-isomer can be distinguished using high field NMR techniques (e.g., ROESY 2D NMR). For example:

example P1 preparation of [5- (2, 4-difluorophenyl) isoxazol-3-yl ] - [ rac- (4R, 7S) -7-methyl-4- (1-methylpyrazol-4-yl) -5, 7-dihydro-4H-thieno [2,3-c ] pyridin-6-yl ] methanone (Compound X.03, table P)

(Racemization)(Compound X.03, table P)

Step A preparation of (1-methylpyrazol-4-yl) - (3-thienyl) methanol

A single neck round bottom flask equipped with a magnetic stirrer bar was charged with 4-iodo-1-methyl-1 h-pyrazole (7.37 g,33.6 mmol) and tetrahydrofuran (92 mL). Under argon atmosphere at 0 ℃, isopropyl magnesium chloride lithium chloride complex (1.3 mol/L) (white suspension) in THF (35 mL) was added dropwise. The mixture was stirred 45 min at 0 ℃. Then, 3-thiophenecarboxaldehyde (3.50 g,30.6 mmol) was added dropwise to the foregoing mixture under an argon atmosphere at 0 ℃. The mixture was stirred at this temperature for 10 min a and then allowed to warm to room temperature and stirred for 1 hour. The reaction mixture was then poured into water (100 mL) and extracted with EtOAc (2×80 mL). The combined organic layers were washed with brine, dried over sodium sulfate and concentrated in vacuo to give the title compound.

LC-MS (method A) retention time 0.56 min,195 (M+H) ⁺

Step B preparation of 2- (1-methylpyrazol-4-yl) -2- (3-thienyl) acetonitrile

A sealed tube equipped with a magnetic stirring bar was charged with (1-methylpyrazol-4-yl) - (3-thienyl) methanol (5.94 g,30.6 mmol) and dichloromethane (245 mL). To this solution were added lithium carbonate (0.456 g,6.12 mmol), trimethylsilyl cyanide (18.7 mL,138 mmol) and iodine (14.2 g,55.0 mmol) successively at room temperature. After stirring for one hour at 35 ℃, the reaction mixture was cooled to room temperature and poured into Na ₂S₂O₃ saturated solution (80 mL) and extracted with dichloromethane (2×60 mL). The combined organic layers were washed with brine, dried over sodium sulfate and concentrated in vacuo. The crude material was purified by silica gel chromatography (20 g SiO ₂, etOAc/cyclohexane gradient) to give the title compound.

LC-MS (method A): retention time 0.75 min,204 (M+H)⁺.¹H NMR (400 MHz, CDCl₃) δ ppm 3.92 (s, 3 H) 5.13 - 5.22 (m, 1 H) 7.00 - 7.08 (m, 1 H) 7.29 - 7.30 (m, 1 H) 7.36 - 7.40 (m, 2 H) 7.42 - 7.47 (m, 1 H).

Step C preparation of 2- (1-methylpyrazol-4-yl) -2- (3-thienyl) ethylamine

A single neck round bottom flask equipped with a magnetic stirring bar was charged with 2- (1-methylpyrazol-4-yl) -2- (3-thienyl) acetonitrile (1.78 g,8.76 mmol) in THF (26 mL). To this solution was added dropwise borane dimethyl sulfide complex (2.65 mL,26.3 mmol) at room temperature under an argon atmosphere, and then the mixture was stirred at 65 ℃ for 1 hour. The reaction mixture was cooled to 0 ℃ and then HCl (6 mol/L,5.87 mL,35.2 mmol) was added dropwise, followed by heating the mixture to 65 ℃ for 1 hour. The mixture was diluted with water (20 mL), basified with 6M NaOH (to pH 12), cooled and extracted with EtOAc (3×20 mL). The combined organic layers were washed with brine, dried over sodium sulfate and concentrated in vacuo to give 2- (1-methylpyrazol-4-yl) -2- (3-thienyl) ethylamine.

LC-MS (method A): retention time 0.25 min,208 (M+H)⁺.¹H NMR (400 MHz, CDCl₃) δ ppm 7.30 - 7.44 (m, 2 H) 7.06 - 7.27 (m, 3 H) 7.00 (br d, J=4.7 Hz, 1 H) 4.06 - 4.30 (m, 1 H) 3.87 (s, 3 H) 3.57 - 3.78 (m, 1 H) 3.21 (br s, 2 H).

Step D preparation of N- [2- (1-methylpyrazol-4-yl) -2- (3-thienyl) ethyl ] acetamide

A single neck round bottom flask equipped with a magnetic stirring bar was charged with 2- (1-methylpyrazol-4-yl) -2- (3-thienyl) ethylamine (1.80 g,8.68 mmol) and saturated aqueous sodium bicarbonate (43 mL). Acetyl chloride (0.71 mL,9.55 mmol) in EtOAc (43 mL) was added dropwise at room temperature with vigorous stirring. The mixture was stirred at room temperature for 15 minutes. The reaction mixture was then extracted with EtOAc (2×20 mL) and the combined organic layers were washed with brine, dried over sodium sulfate and concentrated in vacuo to give N- [2- (1-methylpyrazol-4-yl) -2- (3-thienyl) ethyl ] acetamide.

LC-MS (method A): retention time 0.25 min,234 (M+H)⁺;¹H NMR (400 MHz, CDCl₃) δ ppm 7.37 - 7.41 (m, 1 H) 7.33 (dd, J=5.1, 2.9 Hz, 1 H) 7.21 (s, 1 H) 7.06 (dd, J=1.5, 0.7 Hz, 1 H) 6.99 (dd, J=4.9, 1.3 Hz, 1 H) 5.50 (br s, 1 H) 4.21 (t, J=7.4 Hz, 1 H) 3.89 (s, 3 H) 3.73 (td, J=7.9, 6.0 Hz, 2 H) 1.94 (s, 3 H).

Step E preparation of 7-methyl-4- (1-methylpyrazol-4-yl) -4,5,6, 7-tetrahydrothieno [2,3-c ] pyridine and 4-methyl-7- (1-methylpyrazol-4-yl) -4,5,6, 7-tetrahydrothieno [3,4-c ] pyridine

And

Step 1

A single neck round bottom flask equipped with a magnetic stir bar was charged with N- [2- (1-methylpyrazol-4-yl) -2- (3-thienyl) ethyl ] acetamide (1.73 g,6.94 mmol) and phosphorus oxychloride (7 mL). The mixture was stirred at 60 ℃ for 1 hour. The reaction mixture was cooled to room temperature and slowly poured into a saturated solution of Na ₂CO₃ (20 mL) at 0 ℃ (gas evolved and exotherm |). The mixture was extracted with EtOAc (3×20 mL), the combined organic layers were washed with brine, dried over sodium sulfate and concentrated in vacuo to the title compound as a mixture, which was used in the next step without further purification.

Step 2

A single neck round bottom flask equipped with a magnetic stir bar was charged with the product from step 1 above (913 mg,3.947 mmol) and methanol (12 mL). To this solution was added sodium borohydride (0.233 g,5.92 mmol) at room temperature (gas evolved), and the mixture was then stirred at room temperature for 1 hour. The reaction mixture was poured into water (20 mL) and the mixture extracted with EtOAc (3×20 mL). The combined organic layers were washed with brine, dried over sodium sulfate and concentrated in vacuo to give a mixture of 7-methyl-4- (1-methylpyrazol-4-yl) -4,5,6, 7-tetrahydrothieno [2,3-c ] pyridine and 4-methyl-7- (1-methylpyrazol-4-yl) -4,5,6, 7-tetrahydrothieno [3,4-c ] pyridine.

LC-MS (method A) retention time 0.25 min,234 (M+H) ⁺

Step F preparation of [5- (2, 4-difluorophenyl) isoxazol-3-yl ] - [ rac- (4R, 7S) -7-methyl-4- (1-methylpyrazol-4-yl) -5, 7-dihydro-4H-thieno [2,3-c ] pyridin-6-yl ] methanone (Compound X.03, table P).

A single neck round bottom flask equipped with a magnetic stir bar was charged with a mixture of 7-methyl-4- (1-methylpyrazol-4-yl) -4,5,6, 7-tetrahydrothieno [2,3-c ] pyridine and 4-methyl-7- (1-methylpyrazol-4-yl) -4,5,6, 7-tetrahydrothieno [3,4-c ] pyridine (117 mg,0.265 mmol, mixture from example 1, step E, step 2), etOAc (17 mL), N-diisopropylethylamine (0.88 mL,5.14 mmol) and 5- (2, 4-difluorophenyl) isoxazole 3-carboxylic acid (0.4378 g,1.88 mmol). Then, propionine anhydride (1.82 mL,3.08 mmol) was added dropwise at room temperature, and the mixture was stirred at room temperature. After one hour, the reaction mixture was poured into water (20 mL). The mixture was extracted with EtOAc (2X 20 mL) and the combined organic layers were washed with brine, dried over sodium sulfate and concentrated in vacuo. The crude material was purified by preparative HPLC (preparative HPLC method: automated purification system from waters: 2767 sample manager, 2489 uv/vis detector, 2545 quaternary gradient module MS-RP2: SQDII single quadrupole mass spectrometer equipped with electrospray source: column: BC: phenomenex Gemini NX C, 5 micron particle size, 110 angstrom, 100 x 50 mm. Solvent: a: water; solvent: B: acetonitrile; modifier: formic acid, gradient: 40% B-60% B, run time: 10 min) to give [5- (2, 4-difluorophenyl) isoxazol-3-yl ] - [ rac- (4 r,7 r) -7-methyl-4- (1-methylpyrazol-4-yl) -5, 7-dihydro-4H-thieno [2,3-c ] pyridin-6-yl ] methanone as first eluted product.

LC-MS (method A) retention time 1.05 min,441 (M+H) ⁺

The [5- (2, 4-difluorophenyl) isoxazol-3-yl ] - [ rac- (4 r,7 s) -7-methyl-4- (1-methylpyrazol-4-yl) -5, 7-dihydro-4H-thieno [2,3-c ] pyridin-6-yl ] methanone (x.03) was isolated as a second eluted product.

LC-MS (method A): retention time 1.08 min,441 (M+H)⁺.¹H NMR (400 MHz, CDCl3) δ ppm 7.88 - 8.09 (m, 1 H) 7.30 - 7.49 (m, 2 H) 7.04 - 7.19 (m, 2 H) 6.95 - 7.04 (m, 2 H) 6.67 (d, J=5.1 Hz, 1 H) 5.68 - 6.06 (m, 1 H) 4.53 - 4.98 (m, 1 H) 4.14 - 4.31 (m, 1 H) 3.84 - 4.02 (m, 3 H) 3.00 - 3.47 (m, 1 H) 1.67 - 1.83 (m, 3 H).

Example P2 preparation of [5- (2, 4-difluorophenyl) -1,3, 4-thiadiazol-2-yl ] - [ rac- (4R, 7R) -7-methyl-4- (1-methylpyrazol-4-yl) -5, 7-dihydro-4H-thieno [2,3-c ] pyridin-6-yl ] methanone and [5- (2, 4-difluorophenyl) -1,3, 4-thiadiazol-2-yl ] - [ rac- (4R, 7S) -7-methyl-4- (1-methylpyrazol-4-yl) -5, 7-dihydro-4H-thieno [2,3-c ] pyridin-6-yl ] methanone (Compound X.04, table P)

(Compound X.04, table P)

A single neck round bottom flask equipped with a magnetic stirring bar was charged with a mixture of 7-methyl-4- (1-methylpyrazol-4-yl) -4,5,6, 7-tetrahydrothieno [2,3-c ] pyridine and 4-methyl-7- (1-methylpyrazol-4-yl) -4,5,6, 7-tetrahydrothieno [3,4-c ] pyridine (117 mg,0.265 mmol, mixture from example 1, step E, step 2) (468 mg,2.006 mmol) and toluene (8 mL). Trimethylaluminum (2.01 mL,4.01 mmol) was added stepwise under argon atmosphere at room temperature. The reaction was stirred at room temperature for 20 min, then ethyl 5- (2, 4-difluorophenyl) -1,3, 4-thiadiazole-2-carboxylate (0.5964 g,2.207 mmol) diluted in toluene (8 mL) was added dropwise at room temperature, and the mixture was stirred at 90 ℃ for 24 hours. The reaction mixture was cooled to 0 ℃ and quenched by careful addition of HCl 1M (1 mL). The mixture was diluted with saturated solution of NaHCO ₃ (20 mL) and extracted with EtOAc (3×20 mL). The combined organic layers were washed with brine, dried over sodium sulfate and concentrated in vacuo. The crude material was purified by preparative HPLC (preparative HPLC method: automated purification System from Waters: 2767 sample manager, 2489 UV/visible detector, 2545 Quaternary gradient Module, MS-RP2: SQDII Single quadrupole Mass Spectrometry equipped with electrospray Source, column: MC: phenomenex Gemini NX C, 4 micron particle size, 80 angstrom, 75X 30 mm. Solvent: A: water; solvent: B: acetonitrile; modifier: formic acid: gradient: 40% B-50% B, run time: 10 min) to give [5- (2, 4-difluorophenyl) -1,3, 4-thiadiazol-2-yl ] - [ rac- (4R, 7R) -7-methyl-4- (1-methylpyrazol-4-yl) -5, 7-dihydro-4H-thieno [2,3-c ] pyridin-6-yl ] methanone as the first eluted product

LC-MS (method A) retention time 1.13 min,458 (M+H) ⁺

The second eluted product was [5- (2, 4-difluorophenyl) -1,3, 4-thiadiazol-2-yl ] - [ rac- (4 r,7 s) -7-methyl-4- (1-methylpyrazol-4-yl) -5, 7-dihydro-4H-thieno [2,3-c ] pyridin-6-yl ] methanone (compound x.04, table P).

LC-MS (method A): retention time 1.18 min,458 (M+H)⁺.¹H NMR (400 MHz, CDCl3) δ ppm 8.39 - 8.58 (m, 1 H) 7.31 - 7.58 (m, 2 H) 6.95 - 7.21 (m, 3 H) 6.65 - 6.73 (m, 1 H) 5.84 - 6.66 (m, 1 H) 4.79 - 5.56 (m, 1 H) 4.18 - 4.46 (m, 1 H) 3.87 - 4.03 (m, 3 H) 3.12 - 3.49 (m, 1 H) 1.64 - 1.89 (m, 3 H).

EXAMPLE P3 preparation of [5- (2, 4-difluorophenyl) -1,3, 4-thiadiazol-2-yl ] - [ (4S, 7R) -7-methyl-4- (1-methylpyrazol-4-yl) -5, 7-dihydro-4H-thieno [2,3-c ] pyridin-6-yl ] methanone and 5- (2, 4-difluorophenyl) -1,3, 4-thiadiazol-2-yl ] - [ (4R, 7S) -7-methyl-4- (1-methylpyrazol-4-yl) -5, 7-dihydro-4H-thieno [2,3-c ] pyridin-6-yl ] methanone (Compound X.04, table P)

(The compound X.04 is a compound, table P) (Compound X.04, table P)

The racemic mixture [5- (2, 4-difluorophenyl) -1,3, 4-thiadiazol-2-yl ] - [ rac- (4 r,7 s) -7-methyl-4- (1-methylpyrazol-4-yl) -5, 7-dihydro-4H-thieno [2,3-c ] pyridin-6-yl ] methanone was separated into its enantiomers by preparative SFC HPLC.

Preparation type SFC method:

SEPIATEC PREPARATIVE SFC 100, column DAICEL CHIRALPAK, IB,5 μm, 2.0. 2.0 cm X25 cm. Mobile phase A, CO2-B, meOH isocratic 10% B. Back pressure 150 bar, flow rate 60 ml/min, GLS pump detection UV 285 nm, sample concentration 97 mg in 3 ml MeOH, injection 500. Mu.l.

The following elution peaks were obtained:

[5- (2, 4-difluorophenyl) -1,3, 4-thiadiazol-2-yl ] - [ (4S, 7R) -7-methyl-4- (1-methylpyrazol-4-yl) -5, 7-dihydro-4H-thieno [2,3-c ] pyridin-6-yl ] methanone, retention time (min) about 2.88, chemical purity (area% at 285 nm) > 99, enantiomeric excess (%) > 98.8%

[5- (2, 4-Difluorophenyl) -1,3, 4-thiadiazol-2-yl ] - [ (4R, 7S) -7-methyl-4- (1-methylpyrazol-4-yl) -5, 7-dihydro-4H-thieno [2,3-c ] pyridin-6-yl ] methanone, retention time (min) about 3.30, chemical purity (area% at 285 nm) > 99, enantiomeric excess (%) > 95.3%

EXAMPLE P4 preparation of [5- (2, 4-difluorophenyl) isoxazol-3-yl ] - [ rac- (4S, 7S) -4, 7-dimethyl-4- (1-methylpyrazol-4-yl) -5, 7-dihydrothieno [2,3-c ] pyridin-6-yl ] methanone and [5- (2, 4-difluorophenyl) isoxazol-3-yl ] - [ rac- (4S, 7R) -4, 7-dimethyl-4- (1-methylpyrazol-4-yl) -5, 7-dihydrothieno [2,3-c ] pyridin-6-yl ] methanone (Compound X.02, table P)

(Compound X.02, table P)

Step A preparation of 2- (1-methylpyrazol-4-yl) -2- (3-thienyl) propionitrile

A sealed tube equipped with a magnetic stirring bar and a temperature probe was charged with 2- (1-methylpyrazol-4-yl) -2- (3-thienyl) acetonitrile (2.32 g,11.4 mmol) and THF (46 mL). N-butyllithium (2.5 mol/L,5.5 mL,13.7 mmol) was added dropwise to this solution at-70℃under an argon atmosphere. The mixture was stirred at this temperature for 30 minutes, then methyl iodide (1.08 mL,17.1 mmol) was added dropwise at-78 ℃. The reaction was stirred at-78 ℃ for 5 minutes and then at room temperature for 30 minutes. The reaction mixture was poured into water (60 mL) and extracted with EtOAc (2×50 mL), and the combined organic layers were washed with brine, dried over sodium sulfate and concentrated in vacuo to give 2- (1-methylpyrazol-4-yl) -2- (3-thienyl) propionitrile.

LC-MS (method A): retention time 0.81 min,218 (M+H)⁺.¹H NMR (400 MHz, CDCl₃) δ ppm 2.04 (s, 3 H) 3.91 (s, 3 H) 7.02 - 7.08 (m, 1 H) 7.24 - 7.30 (m, 1 H) 7.31 - 7.34 (m, 1 H) 7.34 - 7.39 (m, 1 H) 7.42 - 7.46 (m, 1 H).

Step B preparation of 2- (1-methylpyrazol-4-yl) -2- (3-thienyl) propan-1-amine

A single neck round bottom flask equipped with a magnetic stirring bar was charged with 2- (1-methylpyrazol-4-yl) -2- (3-thienyl) propanenitrile (2.48 g,11.4 mmol) and THF (34 mL). Borane dimethyl sulfide complex (3.45 mL,34.2 mmol) was added dropwise at room temperature under an argon atmosphere and the mixture was stirred at 65 ℃ for 1 hour. The reaction mixture was cooled to 0 ℃ and then HCL (6 mol/L,7.65 mL,45.9 mmol) (strong gas evolved) was added dropwise and the mixture was stirred at 65 ℃ for 1 hour. The mixture was diluted with water (30 mL), basified with 6M NaOH (pH 12), and extracted with EtOAc (3×20 mL). The combined organic layers were washed with brine, dried over sodium sulfate and concentrated in vacuo to give 2- (1-methylpyrazol-4-yl) -2- (3-thienyl) propan-1-amine.

LC-MS (method A): retention time 0.28 min,222 (M+H)⁺¹H NMR (400 MHz, CDCl₃) δ ppm 7.36 (d, J=0.7 Hz, 1 H) 7.29 (s, 1 H) 7.17 (s, 1 H) 7.04 (dd, J=2.9, 1.5 Hz, 1 H) 6.99 (dd, J=5.1, 1.5 Hz, 1 H) 3.88 (s, 3 H) 3.16 (s, 2 H) 1.65 (s, 3 H).

Step C preparation of N- [2- (1-methylpyrazol-4-yl) -2- (3-thienyl) propyl ] acetamide

A single neck round bottom flask equipped with a magnetic stirring bar was charged with 2- (1-methylpyrazol-4-yl) -2- (3-thienyl) propan-1-amine (1.54 g,6.96 mmol) and saturated aqueous sodium bicarbonate (35 mL). Then, acetyl chloride (0.573 mL,7.65 mmol) dissolved in EtOAc (35 mL) was added dropwise at room temperature with vigorous stirring. The mixture was stirred at room temperature for 15 minutes. The reaction mixture was extracted with EtOAc (2×20 mL) and the combined organic layers were washed with brine, dried over sodium sulfate and concentrated in vacuo to give N- [2- (1-methylpyrazol-4-yl) -2- (3-thienyl) propyl ] acetamide.

LC-MS (method A): retention time 0.68 min,264 (M+H)⁺¹H NMR (400 MHz, CDCl₃) δ ppm 7.29 - 7.36 (m, 2 H) 7.18 (s, 1 H) 7.05 (dd, J=2.9, 1.5 Hz, 1 H) 6.99 (dd, J=4.9, 1.3 Hz, 1 H) 5.22 - 5.38 (m, 1 H) 3.89 (s, 3 H) 3.77 (dd, J=5.8, 5.1 Hz, 2 H) 1.93 (s, 3 H) 1.61 (s, 3 H).

Preparation of 4, 7-dimethyl-4- (1-methylpyrazol-4-yl) -6, 7-dihydro-5H-thieno [2,3-c ] pyridine

A single neck round bottom flask equipped with a magnetic stirring bar was charged with N- [2- (1-methylpyrazol-4-yl) -2- (3-thienyl) propyl ] acetamide (1.46 g,5.54 mmol) and phosphorus oxychloride (5.5 mL). The reaction mixture was stirred at 60 ℃ for 1 hour, cooled to room temperature, and slowly poured into water (30 mL) at 45 ℃. The mixture was basified with Na ₂CO₃ (pH 9) and extracted with EtOAc (3×20 mL). The combined organic layers were washed with brine, dried over sodium sulfate and concentrated in vacuo to give 4, 7-dimethyl-4- (1-methylpyrazol-4-yl) -5H-thieno [2,3-c ] pyridine. It was diluted with methanol (9 mL) and treated in portions with sodium borohydride (0.1728 g,4.384 mmol) at room temperature. The reaction mixture was stirred for 30min and poured into water (20 mL). The mixture was extracted with EtOAc (3×20 mL) and the combined organic layers were washed with brine, dried over sodium sulfate and concentrated in vacuo to give 4, 7-dimethyl-4- (1-methylpyrazol-4-yl) -6, 7-dihydro-5H-thieno [2,3-c ] pyridine.

LC-MS (method A) retention time 0.41 min,248 (M+H) ⁺

Step E preparation of [5- (2, 4-difluorophenyl) isoxazol-3-yl ] - [ rac- (4S, 7S) -4, 7-dimethyl-4- (1-methylpyrazol-4-yl) -5, 7-dihydrothieno [2,3-c ] pyridin-6-yl ] methanone and [5- (2, 4-difluorophenyl) isoxazol-3-yl ] - [ rac- (4S, 7R) -4, 7-dimethyl-4- (1-methylpyrazol-4-yl) -5, 7-dihydrothieno [2,3-c ] pyridin-6-yl ] methanone (Compound X.02, table P).

A single neck round bottom flask equipped with a magnetic stir bar was charged with 4, 7-dimethyl-4- (1-methylpyrazol-4-yl) -6, 7-dihydro-5H-thieno [2,3-c ] pyridine (0.210 g,0.848 mmol), etOAc (9 mL), N-diisopropylethylamine (0.437 mL,2.54 mmol), and 5- (2, 4-difluorophenyl) isoxazole-3-carboxylic acid (0.216 g,0.933 mmol). Then, propylphosphonic anhydride (0.900 mL,1.528 mmol) was added dropwise at room temperature. The reaction mixture was stirred at room temperature for 1 hour and poured into water (20 mL). The aqueous layer was extracted with EtOAc (2×20 mL) and the combined organic layers were washed with brine, dried over sodium sulfate and concentrated in vacuo. The crude material was equipped with an electrospray source by preparative HPLC (preparative HPLC method: automated purification system from Waters: 2767 sample manager, 2489 UV/visible detector, 2545 quaternary gradient Module. MS-RP2: SQDII single quadrupole mass spectrometer). Column MC Phenomenex Gemini NX C, 4 micron particle size, 80 angstroms, 75X 30 mm. The solvent is water, the solvent is acetonitrile, and the modifier is formic acid. Gradient is 40% B-50% B. Run time 10 min) purification to give [5- (2, 4-difluorophenyl) isoxazol-3-yl ] - [ rac- (4 s,7 s) -4, 7-dimethyl-4- (1-methylpyrazol-4-yl) -5, 7-dihydrothieno [2,3-c ] pyridin-6-yl ] methanone as the first eluted product.

LC-MS (method A): retention time 1.14 min,455 (M+H);¹H NMR (600 MHz, CDCl₃) δ ppm 1.61 (s, 3 H) 1.67 (d, J=6.7 Hz, 3 H) 1.69 - 1.70 (m, 1 H) 1.70 (s, 1 H) 3.20 (d, J=12.9 Hz, 1 H) 3.58 (d, J=13.6 Hz, 1 H) 3.72 (s, 3 H) 3.82 (s, 1 H) 3.90 (d, J=15.6 Hz, 1 H) 4.41 (d, J=13.6 Hz, 1 H) 4.92 (d, J=12.9 Hz, 1 H) 5.84 (q, J=6.6 Hz, 1 H) 6.09 (q, J=6.7Hz, 1 H) 6.24 (d, J=3.7 Hz, 1 H) 6.63 (s, 1 H) 6.83 (d, J=5.1 Hz, 1 H) 6.86 (d, J=3.7 Hz, 1 H) 6.99 (s, 1 H) 7.03 - 7.10 (m, 2 H) 7.24 (d, J=5.1 Hz, 1 H) 7.88 -8.05 (m, 1 H).

The second eluted product was [5- (2, 4-difluorophenyl) isoxazol-3-yl ] - [ rac- (4 s,7 r) -4, 7-dimethyl-4- (1-methylpyrazol-4-yl) -5, 7-dihydrothieno [2,3-c ] pyridin-6-yl ] methanone (compound x.02, table P).

LC-MS (method A): retention time 1.16 min,455 (M+H).¹H NMR (600 MHz, CDCl₃) δ ppm 1.56 (s, 5 H) 1.59 (s, 3 H) 1.68 (d, J=6.6 Hz, 5 H) 1.76 (d, J=6.6 Hz, 4 H) 3.26 (d, J=13.2 Hz, 1 H) 3.58 (d, J=13.8 Hz, 2 H) 3.90 (s, 4 H) 3.94 (s, 3 H) 4.53 (d, J=13.8 Hz, 1 H) 4.74 (d, J=13.1 Hz, 1 H) 5.82 (q, J=6.5 Hz, 1 H) 5.99 (q, J=6.6 Hz, 1 H) 6.62 (d, J=5.1 Hz, 1 H) 6.66 (d, J=5.1 Hz, 1 H) 7.14 (d, J=5.1 Hz, 2 H) 7.25 (s, 1 H) 7.30 (s, 1 H) 7.36 (s, 1 H) 7.40 (s, 1 H).

Example P5 preparation of [5- (2, 4-difluorophenyl) isoxazol-3-yl ] - [7- (1, 5-dimethylpyrazol-4-yl) -6, 7-dihydro-4H-thieno [3,2-c ] pyridin-5-yl ] methanone (Compound X.10, table P)

(Compound X.10, table P)

Step A preparation of 7- (1, 5-dimethylpyrazol-4-yl) thieno [3,2-c ] pyridine

Toluene (37.0 mL) and methanol (3.70 mL) were added to a mixture of 7-bromothieno [3,2-c ] pyridine (2.00 g,9.34 mmol,CAS [1535297-40-5 ]), 1, 5-dimethyl-4- (4, 5-tetramethyl-1, 3, 2-dioxaborane-2-yl) pyrazole (4.93 g,22.2 mmol) and potassium carbonate (2.25 g,16.28 mmol) in a microwave vial. The resulting suspension was degassed with argon for several minutes, followed by the addition of tetrakis (triphenylphosphine) palladium (0) (0.86 g,0.74 mmol). The vial was sealed and the reaction mixture was heated to 100 ℃ and stirred under microwave irradiation for 1 hour. After cooling to room temperature, the reaction mixture was partitioned between saturated ammonium chloride solution and EtOAc. The aqueous layer was back extracted twice with EtOAc, and the combined organic layers were dried over sodium sulfate, filtered and concentrated in vacuo. The crude material was purified by silica gel flash chromatography (EtOAc, ethanol 0% to 30%) to give the title compound as a brown solid.

¹H NMR (400 MHz, CDCl₃) δ ppm: 2.39 (s, 3 H) 3.93 (s, 3 H) 7.54 (2d, 2 H) 7.81 (s, 1 H) 8.35 (s, 1 H) 9.08 (s, 1 H).

Preparation of 7- (1, 5-dimethylpyrazol-4-yl) -4,5,6, 7-tetrahydrothieno [3,2-c ] pyridine

To a solution of 7- (1, 5-dimethylpyrazol-4-yl) thieno [3,2-c ] pyridine (intermediate prepared as described in step a) above, 1.70 g,7.72 mmol) in methanol (74 mL) was added sodium cyanoborohydride (2.9 g,46.3 mmol) in portions at room temperature. The reaction mixture was stirred at room temperature until LC-MS showed the reaction was complete. The reaction was then treated with hydrochloric acid (44.0 ml, 1.25M in methanol) until the pH reached 3-4. After stirring at room temperature for two hours, the reaction mixture was then diluted with water and basified with 2N sodium hydroxide. Methanol was evaporated under reduced pressure and the remaining aqueous layer was extracted three times with EtOAc. The combined organic layers were dried over sodium sulfate, filtered and concentrated in vacuo. The resulting brown oil was purified by silica gel flash chromatography (EtOAc, ethanol 0% to 30%) to the title compound, which was used without further purification.

LC-MS (method A) retention time 0.26 min, M/z 234 (M+H) ⁺

Preparation of [5- (2, 4-difluorophenyl) isoxazol-3-yl ] - [7- (1, 5-dimethylpyrazol-4-yl) -6, 7-dihydro-4H-thieno [3,2-C ] pyridin-5-yl ] methanone (Compound X.10, table-T1)

To a solution of 7- (1, 5-dimethylpyrazol-4-yl) -4,5,6, 7-tetrahydrothieno [3,2-c ] pyridine (intermediate prepared as described in step B above, 150 mg,0.64 mmol) and 5- (2, 4-difluorophenyl) isoxazole-3-carboxylic acid (145 mg,0.64 mmol) in EtOAc (1.3 mL) was added a solution of 50% propylphosphonic anhydride in EtOAc (1.02 g,1.60 mmol) followed by N, N-diisopropylethylamine (430 mg,3.20 mmol) at room temperature. The reaction mixture was stirred at room temperature overnight, and then partitioned between water and EtOAc. The aqueous layer was back extracted twice with EtOAc, and the combined organic layers were dried over sodium sulfate, filtered and concentrated in vacuo. The crude material was purified by silica gel flash chromatography (cyclohexane, etOAc 10% to 100%) to give the title compound as a white solid. Melting point 160-161 deg.c.

¹H NMR (400 MHz, CDCl₃) δ ppm: 2.20 + 2.29 (2s, 3 H) 3.33-3.42 + 3.68-3.72 (2m, 1 H) 3.75 1 3.85 (2s, 3 H) 4.28-4.32 + 4.34-4.38 (2m, 1 H) 4.43-4.48 + 4.75-4.80 (2m, 1 H) 4.71-4.76 + 4.82-4.87 (2m, 1 H) 5.20-5.25 + 5.30-5.35 (2m, 1 H) 6.78-6.81 (m, 1 H) 6.90-6.92 (m, 1 H) 6.94-7.13 (m, 3 H) 7.19-7.28 (m, 2 H) 7.93-8.14 (m, 1 H).

EXAMPLE P6 this example illustrates the preparation of [5- (2, 4-difluorophenyl) isoxazol-3-yl ] - [7- (1, 5-dimethylpyrazol-4-yl) -6, 7-dihydro-4H-thiadiazolo [4,5-c ] pyridin-5-yl ] methanone (Compound X.09, table P)

(Compound X.09, table P)

Step A preparation of 3-bromo-4-chloro-5-nitro-pyridine

A mixture of phosphorus oxychloride (21.5 ml,228 mmol) and 3-bromo-5-nitro-pyridin-4-ol (10.0 g,45.6 mmol) in toluene (20 mL) was heated to 90℃for 12 hours. The progress of the reaction was monitored by LC-MS. The reaction mass was cooled to room temperature and the phosphorus oxychloride was removed under reduced pressure. The reaction was quenched with ice, extracted with EtOAc (×3), and the combined organic layers were washed with brine, dried over sodium sulfate and concentrated in vacuo to give 3-bromo-4-chloro-5-nitro-pyridine as a solid.

¹ H NMR (400 MHz, DMSO-d 6) delta ppm 9.20 (s, 1H), 9.17 (s, 1H). LC-MS (method D) retention time 1.08 min,237 (M+H).

Step B preparation of 3-bromo-5-nitro-pyridine-4-thiol

To a solution of 3-bromo-4-chloro-5-nitro-pyridine (2.0 g,8.42 mmol) in methanol (20 mL) was added sodium hydrosulfide (0.96 g,16.8 mmol). The reaction mixture was stirred at room temperature for 2 hours. The reaction was monitored by TLC and LC-MS. After completion, the reaction mixture was concentrated in vacuo to give crude 3-bromo-5-nitro-pyridine-4-thiol (1.80 g,6.90 mmol), which was used as such in the next step.

LC-MS (method D) retention time 0.51 min,235 (M+H).

Step C preparation of 3-amino-5-bromo-pyridine-4-thiol

To a solution of 3-bromo-5-nitro-pyridine-4-thiol (2.0 g,8.50 mmol) in hydrochloric acid (8 mL) was added stannous chloride (3.24 g,17.0 mmol) in water (8 mL). The reaction mixture was stirred at room temperature for 3 hours. After the reaction was completed, the reaction mixture was filtered, and the filtrate was concentrated in vacuo to give crude 3-amino-5-bromo-pyridine-4-thiol (2 g), which was used as such in the next step.

LC-MS (method D) retention time 0.19 min,205 (M+H).

Preparation of 7-Broothiadiazolo [4,5-c ] pyridine

A solution of sodium nitrite (0.52 g,7.60 mmol) in water (20 mL) was added dropwise to a mixture of 3-amino-5-bromo-pyridine-4-thiol (2.0 g,5.85 mmol) in hydrochloric acid (2M) (60 mL,708 mmol) at 0 ℃. The mixture was kept at this temperature for 12 hours. The progress of the reaction was monitored by LC-MS and after completion quenched with sodium bicarbonate, extracted with EtOAc (×3), and the combined organic layers were washed with brine, dried over sodium sulfate and concentrated in vacuo. The resulting crude residue was purified by silica gel chromatography using a cyclohexane/EtOAc eluent system to give 7-bromothiadiazolo [4,5-c ] pyridine.

¹H NMR (400 MHz, CDCl₃ ) Delta ppm 9.90 (s, 1H) 8.84 (s, 1H). LC-MS (method D) retention time 1.05 min,216 (M+H).

Step E preparation of 7- (1, 5-dimethylpyrazol-4-yl) thiadiazolo [4,5-c ] pyridine

A mixture of 7-bromothiadiazolo [4,5-c ] pyridine (0.9 g,4.16 mmol), 1, 5-dimethyl-4- (4, 5-tetramethyl-1, 3, 2-dioxaborane-2-yl) pyrazole (1.46 g,6.24 mmol) and sodium carbonate (1.32 g,12.5 mmol) in 1,4 dioxane (9 mL) and water (2 mL) was degassed 5min with nitrogen. XPhos-Pd-G2 (0.16 g,0.20 mmol,CAS[1310584-14-5) was added to this solution and the reaction mixture was heated to 80℃for 12 hours, then the reaction mass was diluted with water, the combined organic layers were washed with water, brine, the crude residue obtained is purified by trituration with pentane to give 7- (1, 5-dimethylpyrazol-4-yl) thiadiazolo [4,5-C ] pyridine.

¹H NMR (400 MHz, DMSO-d6) δ ppm 9.98 (s, 1 H), 8.76 (s, 1 H), 7.79 (s, 1 H), 3.87 (s, 3 H), 2.40 ( s, 3H).LC-MS（ Method D) retention time 0.88 min,232 (M+H).

Step F preparation of 7- (1, 5-dimethylpyrazol-4-yl) -4,5,6, 7-tetrahydrothiadiazolo [4,5-c ] pyridine

A solution of 7- (1, 5-dimethylpyrazol-4-yl) thiadiazolo [4,5-c ] pyridine (0.17 g,0.73 mmol) in methanol (11 mL) was treated with sodium cyanoborohydride (0.48 g,7.35 mmol) at room temperature and hydrochloric acid (1.25 M,7.35 mL,9.19 mmol in ethanol) was added. The resulting reaction mixture was stirred at room temperature for 12 hours. The reaction was monitored by TLC and LC-MS and after completion it was concentrated in vacuo to give crude 7- (1, 5-dimethylpyrazol-4-yl) -4,5,6, 7-tetrahydrothiadiazolo [4,5-c ] pyridine (0.21 g). The crude compound was used as such in the next step.

LC-MS (method D) retention time 0.17 min,236 (M+H) ⁺

Preparation of [5- (2, 4-difluorophenyl) isoxazol-3-yl ] - [7- (1, 5-dimethylpyrazol-4-yl) -6, 7-dihydro-4H-thiadiazolo [4,5-c ] pyridin-5-yl ] methanone (Compound X.09, table P)

To a solution of 5- (2, 4-difluorophenyl) isoxazole-3-carboxylic acid (0.17 g,0.75 mmol) in acetonitrile (5 mL/mmol) was added N, N-diisopropylethylamine (0.66 mL,3.77 mmol) followed by 1-propanephosphonic anhydride (1.12 mL,1.88 mmol). The resulting solution was stirred under nitrogen for 5 minutes, and then the resulting reaction mass was transferred to another reaction flask containing 7- (1, 5-dimethylpyrazol-4-yl) -4,5,6, 7-tetrahydrothiadiazolo [4,5-c ] pyridine (0.21 g,0.90 mmol) dissolved in 1 mL acetonitrile. The reaction mixture was stirred at room temperature overnight and monitored by TLC and LC-MS. After completion, the reaction mixture was diluted with water, extracted with EtOAc (×3), and the combined organic layers were washed with brine, dried over sodium sulfate and concentrated in vacuo. The resulting crude residue was purified by silica gel chromatography (eluting with cyclohexane/EtOAc) to give [5- (2, 4-difluorophenyl) isoxazol-3-yl ] - [7- (1, 5-dimethylpyrazol-4-yl) -6, 7-dihydro-4H-thiadiazolo [4,5-c ] pyridin-5-yl ] methanone as a solid.

LC-MS (method D) retention time 1.08 min,443.2 (M+H) ⁺

EXAMPLE P7 this example illustrates the preparation of [5- (2, 4-difluorophenyl) isoxazol-3-yl ] - [4- (1-methylpyrazol-4-yl) -5, 7-dihydro-4H-isothiazolo [5,4-c ] pyridin-6-yl ] methanone (Compound X.08, table P)

(Compound X.08, table P)

Step A preparation of 3-bromo-5-fluoro-pyridine-4-carbaldehyde

Lithium diisopropylamide (75 ml,150 mmol) was added dropwise to a solution of 3-bromo-5-fluoro-pyridine (12.0 g,68.1 mmol) in tetrahydrofuran (120 mL) cooled to-78 ℃ at-78 ℃ (the reaction mixture turned brown), and the resulting reaction mixture was stirred at this temperature for 45 minutes. Ethyl formate (56 mL,681 mmol) was added to the reaction mixture over 15 minutes, and the reaction mixture was stirred at-78℃for an additional 1.5 hours. After completion of the reaction (monitored by TLC and GCMS), the reaction mixture was quenched with saturated ammonium chloride solution and the resulting mixture was extracted with EtOAc (×3). The combined organic layers were washed with brine, dried and concentrated in vacuo to give a brown residue which was subjected to flash preparative chromatography (combiflash chromatography) using cyclohexane/EtOAc as eluent. This gives 3-bromo-5-fluoro-pyridine-4-carbaldehyde as a bright yellow solid.

¹H NMR (400 MHz, CDCl₃) δ ppm 10.35 (s, 1 H), 8.74 (s, 1 H), 8.60 (s, 1 H)。

Step B preparation of 3-bromo-5-tert-butylsulfanyl-pyridine-4-carbaldehyde

A mixture of 3-bromo-5-fluoro-pyridine-4-carbaldehyde (6.8 g,30 mmol), potassium carbonate (5.1 g,36 mmol) and 2-methyl-2-propanethiol (3.0 mL,30 mmol) in dry N, N-dimethylformamide (20 mL) was placed in a Teflon vessel and heated to 110℃in a sealed tube for 32 hours. The reaction was cooled to room temperature, water was added, and the mixture was extracted with EtOAc (×3). The combined organic fractions were washed with water, dried over sodium sulfate, filtered, and concentrated in vacuo to give the crude title compound, which was purified using flash chromatography using EtOAc/cyclohexane as eluent to give 3-bromo-5-tert-butylsulfanyl-pyridine-4-carbaldehyde as a yellow oil.

¹H NMR (400 MHz, CDCl₃) δ ppm 10.5 (s, 1 H), 8.85 (s, 1 H), 8.73 (s, 1 H), 1.34 (s, 9 H).

Preparation of 4-bromoisothiazolo [5,4-C ] pyridine

A mixture of 3-bromo-5-tert-butylsulfanyl-pyridine-4-carbaldehyde (3.8 g,12.0 mmol) and hydroxylamine hydrochloride (4.4 g,62.0 mmol) in isopropanol (160 mL) and water (33 mL) was heated to 90℃for 16 hours. The reaction mixture was cooled and the 2-propanol was removed in vacuo. Water was added to the residue followed by saturated aqueous sodium bicarbonate until the pH was about 8. The mixture was extracted with EtOAc (×3) and the combined organic fractions were dried over sodium sulfate, filtered and concentrated in vacuo to give the crude title compound which was used in the next step without further purification. The resulting crude oxime was then suspended in polyphosphoric acid (15 mL) and heated to 110 ℃ for 2 hours. The reaction mixture was cooled to room temperature and extracted with EtOAc, dried over sodium sulfate and concentrated in vacuo. The crude residue was purified by flash preparative chromatography using EtOAc/cyclohexane as eluent to give pure 4-bromoisothiazolo [5,4-c ] pyridine as a white solid.

¹H NMR (400 MHz, CDCl₃) δ ppm 9.29 (s, 1 H), 9.09 (d, J = 0.61 Hz, 1 H), 8.69 (s, 1 H).LC-MS（ Method D) retention time 0.98 min,215 (M+H).

Step D preparation of 4- (1-methylpyrazol-4-yl) isothiazolo [5,4-c ] pyridine

A microwave vial was charged with 4-bromoisothiazolo [5,4-c ] pyridine (0.17 g,0.79 mmol), 1-methyl-1H-pyrazole-4-boronic acid (0.15 g,1.18 mmol), sodium carbonate (0.25 g,2.37 mmol), 1, 4-dioxane (1.7 mL) and water (1.6 mL). The reaction mixture was degassed with nitrogen for 5.0 min, then XPhos-Pd-G2 (0.031 g,0.039 mmol) was added and the mixture was heated to 120 ℃ under microwave radiation for 2 hours. After completion of the reaction (monitored by TLC and LC-MS), the reaction mixture was filtered through celite, washed with EtOAc, and the filtrate was concentrated in vacuo to give a brown residue, which was purified by flash preparative chromatography using EtOAc/cyclohexane eluent system to give pure 4- (1-methylpyrazol-4-yl) isothiazolo [5,4-c ] pyridine as a white solid.

¹H NMR (400 MHz, CDCl₃) δ ppm 9.26 (s, 1 H), 9.19 (s, 1 H), 8.62 (s, 1 H), 7.92 (s, 1 H), 7.81 (s, 1 H), 4.07 (s, 3 H).LC-MS（ Method D) retention time 0.55 min, 217.1 (M+H).

Preparation of 4- (1-methylpyrazol-4-yl) -4,5,6, 7-tetrahydroisothiazolo [5,4-c ] pyridine

A round bottom flask equipped with a magnetic stirring bar was charged with 4- (1-methylpyrazol-4-yl) isothiazolo [5,4-c ] pyridine (0.15 g,0.69 mmol) and methanol (10.4 mL) to give a clear solution. To this solution was added sodium cyanoborohydride (0.45 g,6.93 mmol) in portions at 0 ℃. Then, hydrochloric acid methanol solution (6.9 mL,20.8 mmol,3 mol/L) was added dropwise at room temperature (gas evolution was observed), and the mixture was stirred at room temperature overnight. After the reaction was completed (monitored by TLC and LC-MS), the reaction mixture was stirred with basic resin until the solution was basic to pH paper. The mixture was filtered and washed with methanol, and the clear solution was concentrated to give crude 4- (1-methylpyrazol-4-yl) -4,5,6, 7-tetrahydroisothiazolo [5,4-c ] pyridine (0.1 g,0.43 mmol) as a tan residue.

¹H NMR (400 MHz, DMSO-d6) δ ppm 8.17 (s, 1 H), 7.48 (s, 1 H), 7.29 (s, 1 H), 4.08 (br d, J = 2.9 Hz, 2 H), 3.92 - 4.24 (m, 1 H), 3.77 (s, 3 H), 3.75 (s, 1 H), 3.12 (br dd, J = 12.9, 5.2 Hz, 1 H), 2.73 (dd, J = 12.9, 7.2 Hz, 1 H).LC-MS（ Method D) retention time 0.19 min, 221.1 (M+H).

Step F preparation of [5- (2, 4-difluorophenyl) isoxazol-3-yl ] - [4- (1-methylpyrazol-4-yl) -5, 7-dihydro-4H-isothiazolo [5,4-c ] pyridin-6-yl ] methanone (Compound X.08, table P)

A solution of 5- (2, 4-difluorophenyl) isoxazole-3-carboxylic acid (0.09 g,0.40 mmol) in EtOAc (1.7 mL) was treated with N, N-diisopropylethylamine (0.13 mL,0.73 mmol) with stirring. To this reaction mixture was added 4- (1-methylpyrazol-4-yl) -4,5,6, 7-tetrahydroisothiazolo [5,4-c ] pyridine (0.085 g,0.36 mmol), followed by 1-propanephosphonic anhydride (50 mass%) in EtOAc (0.65 ml,1.1 mmol), and the reaction mixture was stirred at room temperature overnight. After completion of the reaction (monitored by TLC and LC-MS), the reaction mixture was quenched with NaHCO ₃ and extracted with EtOAc (×3). The combined organic layers were dried over sodium sulfate and concentrated in vacuo. The crude material was purified by reverse phase flash chromatography using an acetonitrile/water eluent system to give [5- (2, 4-difluorophenyl) isoxazol-3-yl ] - [4- (1-methylpyrazol-4-yl) -5, 7-dihydro-4H-isothiazolo [5,4-c ] pyridin-6-yl ] methanone as a white solid.

LC-MS (method D) retention time 1.07 min, 428.2 (M+H).

EXAMPLE P8 preparation of [5- (2, 4-difluorophenyl) isoxazol-3-yl ] - [ rac- (4S, 7S) -7- (1, 5-dimethylpyrazol-4-yl) -4-methyl-6, 7-dihydro-4H-thieno [3,2-c ] pyridin-5-yl ] methanone (Compound X.11 in Table P)

Step A preparation of (1, 5-dimethylpyrazol-4-yl) - (2-thienyl) methanol

To a solution of 2-bromothiophene (13.0 g,80.6 mmol) in THF (250 mL) was added isopropylmagnesium chloride lithium chloride complex (1.3 mol/L in THF, 62 mL) at 0 ℃. The resulting mixture was aged 45 min at 0 ℃ and then 1, 5-dimethylpyrazole-4-carbaldehyde (5.0 g,40.3 mmol) in THF (5 mL) was added dropwise over 20: 20 min. The mixture was stirred at this temperature for 10 min hours, allowed to warm to room temperature and stirred for 1 hour. The reaction mixture was quenched with aqueous NH ₄ Cl and extracted with EtOAc. The combined organic layers were washed with brine, dried over sodium sulfate and concentrated in vacuo. The residue was triturated with pentane to give the title compound as an off-white solid.

LC-MS (method A) retention time 0.16 min,209 (M+H) ⁺

Step B preparation of 2- (1, 5-dimethylpyrazol-4-yl) -2- (2-thienyl) acetonitrile

A solution of (1, 5-dimethylpyrazol-4-yl) - (2-thienyl) methanol (2.0 g,9.6 mmol) in acetonitrile (60 mL) was treated with lithium carbonate (0.14 g,1.92 mmol), trimethylsilyl cyanide (5.9 mL,43.2 g) and iodine (4.46 g,17.3 mmol) at 20 ℃. The resulting mixture was warmed to 40 ℃ and stirred at this temperature for 2 h a. After cooling to 20 ℃, the reaction mixture was slowly poured into an aqueous thiosulfate solution and the resulting emulsion extracted with EtOAc. The organic layer was washed with brine, dried over sodium sulfate and concentrated in vacuo to give the title compound.

LC-MS (method A): retention time 0.88 min,218 (M+H)⁺;¹H NMR (400 MHz, CDCl₃) δ ppm 7.44 (s, 1 H) 7.25 - 7.29 (m, 1 H) 7.10 (dt, 1 H) 6.98 (dd, 1 H) 5.26 (s, 1 H) 3.81 (s, 3 H) 2.23 (s, 3 H).

Step C preparation of 2- (1, 5-dimethylpyrazol-4-yl) -2- (2-thienyl) ethylamine

A round bottom flask equipped with a magnetic stir bar was charged with 2- (1, 5-dimethylpyrazol-4-yl) -2- (2-thienyl) acetonitrile (2.50 g,11.5 mmol) in tetrahydrofuran (35 mL). To this solution was added dropwise borane dimethyl sulfide complex (3.48 mL,34.5 mmol) at room temperature under an argon atmosphere, and then the mixture was stirred at 65 ℃ for 2 hours. The reaction mixture was cooled to 0 ℃ and then HCl was added dropwise, followed by heating the reaction mixture to 55 ℃ for 1 hour. The reaction mixture was diluted with water, basified with NaOH (6M) and extracted with EtOAc. The organic layer was washed with brine, dried over sodium sulfate and concentrated in vacuo to give the title compound as a brown gum.

Step C preparation of methyl N- [2- (1, 5-dimethylpyrazol-4-yl) -2- (2-thienyl) ethyl ] carbamate

Methyl chloroformate (0.77 mL,9.92 mmol) and TEA (4.63 mL,33.1 mmol) were added sequentially to a solution of 2- (1, 5-dimethylpyrazol-4-yl) -2- (2-thienyl) ethylamine (1.83 g,8.27 mmol) in THF (35 mL) at 0 ℃. The resulting solution was gradually warmed to 20 ℃ and stirred at this temperature for 3 hours. The reaction mixture was then poured into water and the mixture extracted with EtOAc. The organic phase was washed with brine, dried over sodium sulfate, filtered and concentrated in vacuo to give the title compound as a yellow gum.

LC-MS (method A) retention time 0.96 min,280 (M+H) ⁺

Step D preparation of rac- (4S, 7S) -7- (1, 5-dimethylpyrazol-4-yl) -4-methyl-6, 7-dihydro-4H-thieno [3,2-c ] pyridine-5-carboxylic acid methyl ester

A solution of methyl N- [2- (1, 5-dimethylpyrazol-4-yl) -2- (2-thienyl) ethyl ] carbamate (2.0 g,7.16 mmol) in DCM (20 mL) was cooled to 0℃and treated with trifluoroacetic acid (10 mL) and acetaldehyde (3.15 g,71.6 mmol). The cooling bath was removed and the reaction mixture was warmed to 20 ℃ and stirred at this temperature for 3 h a. Water was then added, the mixture was neutralized with sodium bicarbonate solution and extracted with EtOAc. The organic phase was washed with brine, dried over sodium sulfate, filtered and concentrated in vacuo. The residue was purified by medium pressure chromatography (stationary phase: silica, eluent: cyclohexane, etOAc) to give the title compound.

LC-MS (method A) retention time 1.05 min,306 (M+H) ⁺

Step E preparation of rac- (4S, 7S) -7- (1, 5-dimethylpyrazol-4-yl) -4-methyl-4, 5,6, 7-tetrahydrothieno [3,2-c ] pyridine

Iodotrimethylsilane (1.52 mL,10.8 mmol) is added to a solution of rac- (4 s,7 s) -7- (1, 5-dimethylpyrazol-4-yl) -4-methyl-6, 7-dihydro-4H-thieno [3,2-C ] pyridine-5-carboxylic acid methyl ester (1.10 g,3.6 mmol) in 1, 2-dichloroethane (18 mL) at 20 ℃. The resulting solution was warmed to 60 ℃ and stirred at this temperature for 3h a. The reaction was then cooled to room temperature and slowly poured into aqueous sodium bicarbonate. The resulting emulsion was extracted with EtOAc, the organic phase was washed with aqueous thiosulfate and brine, dried over sodium sulfate, filtered and concentrated in vacuo to give the title compound.

LC-MS (method A): retention time 0.18 min,248 (M+H)⁺;¹H NMR (400 MHz, CDCl₃) δ ppm 7.15 (d, 1 H) 7.09 (s, 1 H) 6.83 (d, 1 H) 4.21 (dd, 1 H) 4.07 - 4.16 (m, 1 H) 3.79 (s, 3 H) 3.30 (dd, 1 H) 3.10 (dd, 1 H) 2.21 (s, 3 H) 1.51 (d, 3 H).

Step F preparation of [5- (2, 4-difluorophenyl) isoxazol-3-yl ] - [ rac- (4S, 7S) -7- (1, 5-dimethylpyrazol-4-yl) -4-methyl-6, 7-dihydro-4H-thieno [3,2-c ] pyridin-5-yl ] methanone (Compound X.11 in Table P)

A mixture of rac- (4S, 7S) -7- (1, 5-dimethylpyrazol-4-yl) -4-methyl-4, 5,6, 7-tetrahydrothieno [3,2-C ] pyridine (0.25 g,0.81 mmol) and 5- (2, 4-difluorophenyl) isoxazole-3-carboxylic acid (0.20 g,0.89 mmol) in EtOAc (4 mL) was treated with N, N-diisopropylethylamine (0.45 mL,2.4 mmol) and T3P (50% 1.43 mLm 2.4 mmol in EtOAc) at 20 ℃. The resulting solution was stirred at 20 ℃ for 2h and then diluted with water. The mixture was extracted with EtOAc, the organic phase was washed with brine, dried over sodium sulfate, filtered and concentrated in vacuo. The residue was purified by preparative reverse phase HPLC to give the title compound as a white solid.

LC-MS (method A) retention time 1.16 min,456 (M+H) ⁺;¹H NMR (400 MHz, CDCl₃) delta ppm (this compound was present as a mixture of rotamers in a ratio of about 2:1, chemical shifts of the major rotamers were reported) ) 7.94-8.02 (m, 1 H) 7.36 (s, 1H) 7.21 (d, 1 H) 7.01-7.06 (m, 3H) 6.89 (d, 1 H) 5.78 (m, 1H) 4.52 (dd, 1 H) 4.38 (dd, 1 H) 3.84 (s, 3 H) 3.38 (m, 1 H) 2.32 (s, 3H) 1.63 (d, 3 H).

Examples of the synthesized compounds of formula (I) (component a) are shown in table P.

Table P synthetic compounds according to the compounds of formula (I) X.01 to X.11 and spectral and physicochemical data (Table X above)

Biological example of component A

EXAMPLE B1 Alternaria solani/tomato/leaf discs (early blight)

Tomato leaf disc cultivar beratio (Baby) was placed on agar in multiwell plates (24-well format) and sprayed with formulated test compound diluted in water. 2 days after application, leaf discs were inoculated with a spore suspension of the fungus. Inoculated leaf discs were incubated in a climatic chamber under a light regimen of 12/12 h (light/dark), at 23 ℃/21 ℃ (day/night) and 80% rh, and the activity of the compounds was assessed as percent disease control compared to untreated when appropriate levels of disease damage occurred on untreated test leaf discs (5 to 7 days post-application). The following compounds gave at least 80% control of Alternaria solani at 200 ppm, X.01, X.02, X.03, X.04, X.05, X.06, X.08, X.09, X.10, X.11 when compared to untreated controls showing extensive disease development under the same conditions

EXAMPLE B2 Botrytis cinerea (Botryotinia fuckeliana) Fusarium (Botrytis cinerea))/liquid culture (Botrytis cinerea)

Fungal conidia from frozen storage are directly mixed into a nutrient broth (Vogels) broth. After placing the (DMSO) solution of the test compound in a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates were incubated at 24 ℃ and inhibition of growth was determined photometrically 3 to 4 days after application. X.01, X.02, X.03, X.04, X.05, X.06, X.07, X.08, X.10, X.11, the following compounds gave at least 80% control of Botrytis cinerea at 20 ppm when compared to untreated controls showing extensive disease progression under the same conditions

EXAMPLE B3 Confucius cucurbitae (anthracnose of melon)/liquid culture (anthracnose)

Fungal conidia from frozen storage are directly mixed into the nutrient broth (PDB-potato dextrose broth). After placing the (DMSO) solution of the test compound in a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates were incubated at 24 ℃ and inhibition of growth was measured photometrically 3 to 4 days after application. X.01, X.02, X.03, X.04, X.05, X.06, X.07, X.08, X.09, X.10, X.11, the following compounds gave at least 80% control of Consumer melon at 20 ppm when compared to untreated controls showing extensive disease progression under the same conditions

Example B4 powdery mildew (Blumeria graminis f, sp. Tritici) (powdery mildew (ERYSIPHE GRAMINIS f, sp. Tritici))/wheat/leaf discs preventative (powdery mildew on wheat)

Wheat leaf segment cultivar candler (Kanzler) was placed on agar in multiwell plates (24-well format) and sprayed with formulated test compound diluted in water. Leaf discs were inoculated 1 day after application by shaking powdery mildew infected plants over these test plates. Inoculated leaf discs were incubated in a climatic chamber under a light regimen of 24 h darkness followed by 12h light/12 h darkness at 20 ℃ and 60% rh, and the activity of the compounds was assessed as percent disease control compared to untreated when appropriate levels of disease damage occurred on untreated control leaf segments (6 to 8 days post-application). The following compounds gave at least 80% control of powdery mildew at 200 ppm, X.01, X.03, X.04, X.05, X.06, X.09, X.10, X.11 when compared to untreated controls showing extensive disease development under the same conditions

EXAMPLE B5 Fusarium yellow/liquid culture (scab)

Fungal conidia from frozen storage are directly mixed into the nutrient broth (PDB-potato dextrose broth). After placing the (DMSO) solution of the test compound in a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates were incubated at 24 ℃ and inhibition of growth was determined photometrically 3 to 4 days after application. The following compounds gave at least 80% control of Fusarium flavum at 20 ppm, X.01, X.03, X.04, X.05, X.10 when compared to untreated controls showing extensive disease progression under the same conditions

EXAMPLE B6 Fusarium yellow/wheat/spike preventative (scab)

Wheat spike cultivar mangrove (Monsun) was placed on agar in multiwell plates (24-well format) and sprayed with formulated test compound diluted in water. The spikelets were inoculated with a spore suspension of the fungus 1 day after application. The inoculated spikes were incubated in a climatic chamber under a light regimen of 72h half darkness followed by 12 h light/12 h darkness at 20 ℃ and 60% rh, and the activity of the compounds was assessed as percent disease control compared to untreated when appropriate levels of disease damage occurred on untreated test spikes (6 to 8 days post-application). The following compounds gave at least 80% control of Fusarium flavum at 200 ppm, X.04, when compared to untreated controls showing extensive disease progression under the same conditions

EXAMPLE B7 Septoria nodorum (Phaeosphaeria nodorum, septoria nodorum)/wheat/leaf disc preventative (Leptosphaeria nodorum)

Wheat leaf segment cultivar candler (Kanzler) was placed on agar in multiwell plates (24-well format) and sprayed with formulated test compound diluted in water. 2 days after application, leaf discs were inoculated with a spore suspension of the fungus. Inoculated test leaf discs were incubated in a climatic chamber under a light regimen of 12 h light/12 h darkness at 20 ℃ and 75% rh, and the activity of the compounds was assessed as percent disease control compared to untreated when appropriate levels of disease damage occurred on untreated test leaf discs (5 to 7 days post-application). X.01, X.02, X.03, X.04, X.05, X.06, X.07, X.08, X.09, X.10, X.11 give at least 80% control of Septoria nodorum at 200 ppm when compared to untreated controls showing extensive disease progression under the same conditions

EXAMPLE B8 Fusarium snow rot (Monographella nivalis) (Rhizoctonia solani)/liquid culture (cereal root rot)

Fungal conidia from frozen storage are directly mixed into the nutrient broth (PDB-potato dextrose broth). After placing the (DMSO) solution of the test compound in a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates were incubated at 24 ℃ and inhibition of growth was determined photometrically 4 to 5 days after application. The following compounds gave at least 80% control of C.snow rot at 20 ppm, X.01, X.02, X.07, X.08, X.09, X.10, X.11 when compared with untreated controls showing extensive disease development under the same conditions

EXAMPLE B9 Phlebopus (cercospora arachidis)/liquid culture (early leaf spot)

Fungal conidia from frozen storage are directly mixed into the nutrient broth (PDB-potato dextrose broth). After placing the (DMSO) solution of the test compound in a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates were incubated at 24 ℃ and inhibition of growth was determined photometrically 4 to 5 days after application. X.01, X.02, X.03, X.04, X.05, X.06, X.07, X.10, X.11, the following compounds gave at least 80% control of F.tumefaciens at 20 ppm when compared to untreated controls showing extensive disease development under the same conditions

EXAMPLE B10 Pyricularia oryzae (Magnaporthe grisea) (Pyricularia oryzae)/rice/leaf discs preventive (Pyricularia oryzae)

Rice leaf segment cultivar Baolila (Ballila) was placed on agar in multiwell plates (24 well format) and sprayed with formulated test compound diluted in water. 2 days after application, the leaf segments were inoculated with a spore suspension of the fungus. Inoculated leaf sections were incubated at 22 ℃ and 80% rh in a climatic chamber under a light regimen of 24 h darkness followed by 12 h light/12 h darkness, and the activity of the compounds was assessed as percent disease control compared to untreated when appropriate levels of disease damage occurred in untreated test leaf sections (5 to 7 days post-application). The following compounds gave at least 80% control of Pyricularia oryzae at 200 ppm when compared to untreated controls showing extensive disease development under the same conditions X.06

EXAMPLE B11 prevention of Pyricularia/barley/leaf discs (net blotch)

Barley leaf segment cultivar haloso (Hasso) was placed on agar in multiwell plates (24 well format) and sprayed with formulated test compound diluted in water. 2 days after application, the leaf segments were inoculated with a spore suspension of the fungus. Inoculated leaf sections were incubated in a climatic chamber under a light regimen of 12 h light/12 h darkness at 20 ℃ and 65% rh, and the activity of the compounds was assessed as disease control compared to untreated when appropriate levels of disease damage occurred on untreated control leaf sections (5 to 7 days post-application). The following compounds gave at least 80% control of Rhizoctonia at 200 ppm, X.01, X.03, X.04, X.05, X.06, X.09, X.10, X.11 when compared to untreated controls showing extensive disease progression under the same conditions

EXAMPLE B12 Nuclear disk fungus/liquid culture (Cotton-like rot)

The mycelium fragments of the newly grown liquid culture of the fungus were directly mixed into the nutrient broth (PDB-potato dextrose broth). After placing the (DMSO) solution of test compound in a microtiter plate (96-well format), the nutrient broth containing the fungal material is added. The test plates were incubated at 24 ℃ and inhibition of growth was determined photometrically 3 to 4 days after application. The following compounds gave at least 80% control of sclerotinia at 20 ppm, X.01, X.02, X.03, X.05, X.06, X.10, X.11 when compared to untreated controls showing extensive disease progression under the same conditions

EXAMPLE B13 Mycosphaerella graminea (Septoria tritici)/liquid culture (leaf blight (Septoria blotch))

Fungal conidia from frozen storage are directly mixed into the nutrient broth (PDB-potato dextrose broth). After placing the (DMSO) solution of the test compound in a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates were incubated at 24 ℃ and inhibition of growth was determined photometrically 4 to 5 days after application. X.01, X.02, X.03, X.04, X.05, X.06, X.07, X.08, X.09, X.10, X.11, the following compounds gave at least 80% control of Mycosphaerella graminea at 20 ppm when compared to untreated controls showing extensive disease progression under the same conditions

Biological examples of fungicidal mixtures

Example M-B1 Botrytis cinerea (Botrytis cinerea)

Fungal conidia from frozen storage are directly mixed into nutrient broth (Vogel's) broth. After placing the (DMSO) solution of the test compound in a microtiter plate (96-well format), the nutrient broth containing the fungal spores is added. The test plates were incubated at 24 ℃ and after 72 hours growth inhibition was determined photometrically and visually. In this test system, the following mixture composition (A: B) gave at least 70% disease control at the reported concentrations (in ppm).

The term "component A" refers to a compound having the formula (I).

。

Claims

1. A fungicidal composition comprising components (A) and (B) as active ingredients, wherein component (A) is a compound having formula (I):

(I)

in

^R1 is selected from hydrogen, _C1 - _C3 -alkyl, or _C3 - _C6 -cycloalkyl;

^R2 is selected from hydrogen, halogen, _C1 - _C3 -alkyl, _C1 - _C4 -haloalkyl, or _C3 - _C6 -cycloalkyl;

^R3 is hydrogen;

^R4 is selected from hydrogen or _C1 - _C3 -alkyl;

^R5 and ^R6 are hydrogen;

^R7 is selected from hydrogen, _C1 - _C3 -alkyl, _C1 - _C3 -alkylcarbonyl or _C1 - _C3 -alkoxycarbonyl;

^Z1 is selected from phenyl, or 5-membered or 6-membered heteroaryl, wherein any one of the 5-membered or 6-membered heteroaryl contains 1, 2, or 3 heteroatoms individually selected from N, O, or S, provided that only one is selected from O or S; and wherein the phenyl and any one of the 5-membered or 6-membered heteroaryl are unsubstituted or substituted by 1, 2, or 3 substituents independently selected from halogen, cyano, _C1 - _C3 -alkyl, _C1 - _C2 -haloalkyl, or _C1 - _C3 -alkoxy.

^X1 , ^X2 , and ^X3 are independently selected from CH, N, or S, provided that one of ^X1 , ^X2 , and ^X3 is S; and

^A1 , ^A2 , and ^A3 are independently selected from CH, N, O, or S, provided that at least one of ^A1 , ^A2 , and ^A3 is selected from N, O, or S, and no more than one of ^A1 , ^A2 , and ^A3 is O or S; or a salt or N-oxide thereof.

and

Component (B) is selected from the following compounds: fluopyram, benzovindiflupyr, bifenthiophanate-methyl, fluopyram, pyraclostrobin, fluopyram, pyraclostrobin, fluopyram, fluopyram, thiamethoxam, bifenthiamethoxam, isopyram, indapyram, isopyram, fluopyram, triflupyridam, flupyraclostrobin, imidacloprid, toluene-methyl. Azoxystrobin, azoxystrobin, oxadiazon, methyl pyraclostrobin, oxadiazon, azoxystrobin, tetrazoxystrobin, indoxazolidinium, cyazofamid, pyridaben, pyridabenamide, pyridabenamide, pyrimethanil, fluazinam, triphenyltin hydroxide, silthiamethoxam, butylmorpholine, benzyl benzoate, spirocyclam, cyclophosphamide, imazalil, azoxystrobin, furazolidone, cycloconazole, difenoconazole, flutriafol Fenoxacol, hexaconazole, tebuconazole, cyproconazole, propiconazole, tebuconazole, flufenoxuron, tebuconazole, fenbendazole, prothioconazole, fluopyram, chlorfluazuron, fluoxazuron, isopyram, fluopyram, metalaxyl-M, pyrimethanil, pyrimethanil, kasugamycin, mancozeb, copper fungicide, sulfur, thiamethoxam, captan, chlorothalonil, dithiamethoxam, quinoxalic acid Propoxyquin, fludioxonil, iprodione, procymidone, thiabendazole, benomyl, benomylone, fluopyram, cymoxanil, fluoxazin, fluoxazinol, aramidoylbenzene-S-methyl, isothiazinol, phosphorous acid, cycloflufenoxam, isobutylethoxyquin, tetrazolium pyrazol, tricyclazole, N-methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3 [-yl]phenyl]methyl]cyclopropanecarboxamide, N,2-dimethoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propionamide, 1-methoxy-3-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, 1,3-dimethoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, N-[(1R)-1-benzyl-3-chloro-1-methyl-but-3-enyl]-8-fluoro-quinoline-3-carboxamide, N-[(1S)-1-benzyl-3-chloro-1-methyl-but-3-enyl]-8-fluoro-quinoline-3-carboxamide, N-[(1R)-1- [Benzyl-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide, N-[(1S)-1-benzyl-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide, N-[(1R)-1-benzyl-1,3-dimethyl-butyl]-7,8-difluoro-quinoline-3-carboxamide, N-[(1S)-1-benzyl-1,3-dimethyl-butyl]-7,8-difluoro-quinoline-3-carboxamide, 8-fluoro-N-[(1R)-1-[(3-fluorophenyl)methyl]-1,3-dimethyl-butyl]quinoline-3-carboxamide, 8-fluoro-N-[(1S)-1-[(3-fluorophenyl)methyl]-1,3-dimethyl-butyl]quinoline-3-carboxamide, N-[(1R] (1S)-1-benzyl-1,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide, N-[(1S)-1-benzyl-1,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide, N-((1R)-1-benzyl-3-chloro-1-methyl-but-3-enyl)-8-fluoro-quinoline-3-carboxamide, N-((1S)-1-benzyl-3-chloro-1-methyl-but-3-enyl)-8-fluoro-quinoline-3-carboxamide, (Z)-3-methoxy-2-[2-methyl-5-[4-(trifluoromethyl)triazol-2-yl]phenoxy]prop-2-enoic acid methyl ester, (Z)-3-methoxy-2-[2-methyl-5-(4-propyltriazol-2-yl)phenoxy]prop-2-enoic acid methyl ester, (Z)-2-[ methyl 5-(3-isopropylpyrazole-1-yl)-2-methyl-phenoxy]-3-methoxy-prop-2-enoate, methyl (Z)-3-methoxy-2-[2-methyl-5-(3-propylpyrazole-1-yl)phenoxy]prop-2-enoate, methyl (Z)-3-methoxy-2-[2-methyl-5-[3-(trifluoromethyl)pyrazole-1-yl]phenoxy]prop-2-enoate, methyl (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate, methyl (Z)-2-(5-cyclopentyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate, methyl 2-[cyano-(2,6-difluoro-4-pyridinyl)amino]-5-methyl-N-spiro[3.4]oct-3-yl-thiazol-4 -Formamide, 2-[cyano-(2,6-difluoro-4-pyridinyl)amino]-N-(2,2-dimethylcyclobutyl)-5-methyl-thiazolyl-4-carboxamide, 2-[cyano-(2,6-difluoro-4-pyridinyl)amino]-N-hexyl-5-methyl-thiazolyl-4-carboxamide, 2-[(2,6-difluoro-4-pyridinyl)-(2-methoxyacetyl)amino]-N-(2,2-dimethylcyclobutyl)-5-methyl-thiazolyl-4-carboxamide, 2-[(2,6-difluoro-4-pyridinyl)-(tetrahydropyran-4-carbonyl)amino]-N-(2,2-dimethylcyclobutyl)-5-methyl-thiazolyl-4-carboxamide, 2-[(2,6-difluoro-4-pyridinyl)-(oxetane-3-carbonyl)amino]- N-(2,2-Dimethylcyclobutyl)-5-methyl-thiazol-4-carboxamide, 2-[(2,6-difluoro-4-pyridinyl)-(tetrahydrofuran-3-carbonyl)amino]-N-(2,2-dimethylcyclobutyl)-5-methyl-thiazol-4-carboxamide, 2-[acetyl-(2,6-difluoro-4-pyridinyl)amino]-N-(2,2-dimethylcyclobutyl)-5-methyl-thiazol-4-carboxamide, 2-[(2,6-difluoro-4-pyridinyl)-(2-methylpropionyl)amino]-N-(2,2-dimethylcyclobutyl)-5-methyl-thiazol-4-carboxamide, TAEGRO® (Bacillus amyloliquefaciens strain FZB24), Melaleuca alternifolia oil (tea tree plant Melaleuca alternifolia extract as Timorex) Gold® (available commercially, a broad-spectrum plant-based fungicide), Polygonum cuspidatum extract (available commercially as REGALIA®), plant extracts based on Alpinia serratifolia extract (available commercially as BOTRISTOP®), and gold basidiosin A.

2. The antifungal composition according to claim 1, wherein component (A) is a compound having formula (I), wherein ^R1 is selected from _C1 - _C3 -alkyl; ^R2 is selected from hydrogen or _C1 - _C3 -alkyl; and ^R3 is hydrogen;

^R4 is selected from hydrogen or methyl; ^R5 and ^R6 are hydrogen; ^R7 is selected from hydrogen or _C1 - _C3 -alkyl; ^Z1 is selected from 2,4-difluorophenyl, 3,5-difluoro-2-pyridyl, 2-fluorophenyl, or 4-fluorophenyl; ^X1 is CH, ^X2 is CH, and ^X3 is S; or ^X1 is S, ^X2 is CH, and ^X3 is CH; or ^X1 is CH, ^X2 is N, and ^X3 is S; or ^X1 is S, ^X2 is N, and ^X3 is N; and ^A1 , ^A2 , and ^A3 are independently selected from CH, N, O, or S, provided that at least one of ^A1 , ^A2 , and ^A3 is selected from N, O, or S, and no more than one of ^A1 , ^A2 , and ^A3 is O or S.

3. The antifungal composition according to claim 1 or claim 2, wherein component (A) is a compound having the formula (I-A).

(IA)

Wherein ^R1 , ^R2 , ^R3 , ^R4 , ^R5 , ^R6 , ^R7 , ^X1 , ^X2 , ^X3 and ^Z1 correspond to the same definition as for compounds having formula (I) according to claim 1 or claim 2, and A is selected from A2, A9, or A10;

The crossed lines represent bonds to C (=O) groups and the arrows represent bonds to Z ¹ groups.

4. The antifungal composition according to any one of claims 1 to 3, wherein component (A) is selected from [5-(2,4-difluorophenyl)-1,3,4-thiadiazol-2-yl]-[(4R,7S)-4,7-dimethyl-4-(1-methylpyrazol-4-yl)-5,7-dihydrothiopheno[2,3-c]pyridin-6-yl] methyl ketone (X.01); [5-(2,4-difluorophenyl)isoxazo-3-yl]-[racemic-(4S,7R)-4,7-dimethyl-4-(1-methylpyrazole-4-yl)-5,7-dihydrothieno[2,3-c]pyridin-6-yl] ketone (X.02); [5-(2,4-difluorophenyl)isoxazo-3-yl]-[racemic-(4R,7S)-7-methyl-4-(1-methylpyrazole-4-yl)-5,7-dihydro-4H-thieno[2,3-c]pyridin-6-yl] ketone (X.03); [5-(2,4-difluorophenyl)-1,3,4-thiadiazol-2-yl]-[racemic-(4R,7S)-7-methyl-4-(1-methylpyrazole-4-yl)-5,7-dihydro-4H-thieno[2,3-c]pyridin-6-yl] ketone (X.04); [5-(2,4-difluorophenyl)-1,3,4-thiadiazol-2-yl]-[4-methyl-4-(1-methylpyrazole-4-yl)-5,7-dihydrothieno[2,3-c]pyridin-6-yl] ketone (X.05); [5-(2,4-difluorophenyl)isoxazol-3-yl]-[4-methyl-4-(1-methylpyrazole-4-yl)-5,7-dihydrothiopheno[2,3-c]pyridin-6-yl] ketone (X.06); [5-(2,4-difluorophenyl)isoxazol-3-yl]-[7-methyl-7-(1-methylpyrazole-4-yl)-4,6-dihydrothiopheno[3,2-c]pyridin-5-yl] ketone (X.07); [5-(2,4-difluorophenyl)isoxazol-3-yl]-[4-(1-methylpyrazole-4-yl)-5,7-dihydro-4H-isothiazo[5,4-c]pyridin-6-yl] ketone (X.08); [5-(2,4-difluorophenyl)isoxazo-3-yl]-[7-(1,5-dimethylpyrazol-4-yl)-6,7-dihydro-4H-thiadiazo[4,5-c]pyridin-5-yl] methyl ketone (X.09); [5-(2,4-difluorophenyl)isoxazo-3-yl]-[7-(1,5-dimethylpyrazol-4-yl)-6,7-dihydro-4H-thienro[3,2-c]pyridin-5-yl] methyl ketone (X.10), or [5-(2,4-difluorophenyl)isoxazol-3-yl]-[racemic-(4S,7S)-7-(1,5-dimethylpyrazol-4-yl)-4-methyl-6,7-dihydro-4H-thieno[3,2-c]pyridin-5-yl] methyl ketone (X.11).

5. The fungicidal composition according to any one of claims 1 to 4, wherein component (B) is a compound selected from the group consisting of: fluopyram, benzovindiflupyr, bifenthiophanate-methyl, fluopyram, pyraclostrobin, pyraclostrobin, fluopyram, fluopyram, thiafluzamide, bifenthiophanate-methyl, isopropoxyfenopyram, indapoxetine, fluopyram, triflupyridamole, azoxystrobin, oxadiazon, pyraclostrobin, tetrazoxystrobin, pyridamole, pyridamole, pyridamole amide, fluopyram, benzyloxydine, cyclopyridamole, cycloconazole, difenoconazole, tebuconazole, tebuconazole Propiconazole, Tebuconazole, Flufenoxam, Prothioconazole, Chlorothalonazole, Fluoxadazole, Isopropylquinoline, Fluoxadazole, Metalaxyl-M, Azoxystrobin, Pyrimethanil, Mancozeb, Copper compounds (different salts), Sulfur, Captan, Chlorothalonil, Dithiamethoxam, Propoxyquinoline, Fludioxonil, Benomyl, Fluoxadixyl sulfonate, Aramaic acid-S-methyl, Phosphorous acid, Cyclofluoromethane, Tricyclazole, N-Methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazole -3-yl]phenyl]methyl]cyclopropane formamide, N,2-dimethoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propionamide, 1-methoxy-3-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, 1,3-dimethoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, N-[ (1R)-1-benzyl-3-chloro-1-methyl-but-3-enyl]-8-fluoro-quinoline-3-carboxamide, N-[(1S)-1-benzyl-3-chloro-1-methyl-but-3-enyl]-8-fluoro-quinoline-3-carboxamide, N-[(1R)-1-benzyl-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3-carboxamide, N-[(1S)-1-benzyl-3,3,3-trifluoro-1-methyl-propyl]-8-fluoro-quinoline-3 -Formamide, N-[(1R)-1-benzyl-1,3-dimethyl-butyl]-7,8-difluoro-quinoline-3-carboxamide, N-[(1S)-1-benzyl-1,3-dimethyl-butyl]-7,8-difluoro-quinoline-3-carboxamide, 8-fluoro-N-[(1R)-1-[(3-fluorophenyl)methyl]-1,3-dimethyl-butyl]quinoline-3-carboxamide, 8-fluoro-N-[(1S)-1-[(3-fluorophenyl)methyl]-1,3-dimethyl-butyl]quinoline-3-carboxamide, 8-fluoro-N-[(1S)-1-[(3-fluorophenyl)methyl]-1,3-dimethyl [(1R)-1-benzyl-1,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide, N-[(1S)-1-benzyl-1,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide, N-((1R)-1-benzyl-3-chloro-1-methyl-but-3-enyl)-8-fluoro-quinoline-3-carboxamide, N-((1S)-1-benzyl-3-chloro-1-methyl-but-3-enyl)-8-fluoro-quinoline-3-carboxamide - Quinoline-3-carboxamide, (Z)-3-methoxy-2-[2-methyl-5-[4-(trifluoromethyl)triazol-2-yl]phenoxy]prop-2-enoic acid methyl ester, (Z)-3-methoxy-2-[2-methyl-5-(4-propyltriazol-2-yl)phenoxy]prop-2-enoic acid methyl ester, (Z)-2-[5-(3-isopropylpyrazole-1-yl)-2-methyl-phenoxy]-3-methoxy-prop-2-enoic acid methyl ester, (Z)-3-methoxy-2-[2 Methyl 5-(3-propylpyrazole-1-yl)phenoxy]prop-2-enoate, (Z)-3-methoxy-2-[2-methyl-5-[3-(trifluoromethyl)pyrazole-1-yl]phenoxy]prop-2-enoate, (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate, (Z)-2-(5-cyclopentyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoate (these compounds can be derived from WO4) Prepared by the method described in 2020/193387), 2-[cyano-(2,6-difluoro-4-pyridyl)amino]-5-methyl-N-spiro[3,4]oct-3-yl-thiazolyl-4-carboxamide, 2-[cyano-(2,6-difluoro-4-pyridyl)amino]-N-(2,2-dimethylcyclobutyl)-5-methyl-thiazolyl-4-carboxamide, 2-[cyano-(2,6-difluoro-4-pyridyl)] [Amino]-N-hexyl-5-methyl-thiazol-4-carboxamide, 2-[(2,6-difluoro-4-pyridyl)-(2-methoxyacetyl)amino]-N-(2,2-dimethylcyclobutyl)-5-methyl-thiazol-4-carboxamide, 2-[(2,6-difluoro-4-pyridyl)-(tetrahydropyran-4-carbonyl)amino]-N-(2,2-dimethylcyclobutyl)-5-methyl-thiazol-4-carboxamide, 2-[(2,6-difluoro-4-pyridinyl)-(oxetane-3-carbonyl)amino]-N-(2,2-dimethylcyclobutyl)-5-methyl-thiazol-4-carboxamide, 2-[(2,6-difluoro-4-pyridinyl)-(tetrahydrofuran-3-carbonyl)amino]-N-(2,2-dimethylcyclobutyl)-5-methyl-thiazol-4-carboxamide, 2-[acetyl-(2,6-difluoro-4-pyridinyl)] [Amino]-N-(2,2-dimethylcyclobutyl)-5-methyl-thiazole-4-carboxamide, 2-[(2,6-difluoro-4-pyridinyl)-(2-methylpropionyl)amino]-N-(2,2-dimethylcyclobutyl)-5-methyl-thiazole-4-carboxamide, TAEGRO® (i.e., Bacillus amyloliquefaciens strain FZB24), Melaleuca alternifolia oil (Melaleuca alternifolia extract from the tea plant (commercially available as Timorx Gold®, a broad-spectrum phytofungicide)), Polygonum cuspidatum extract (commercially available as REGALIA®), plant extracts based on Alternaria scutellariae (commercially available as BOTRISTOP®), or basidiosin A.

6. The fungicidal composition according to any one of claims 1 to 5, wherein component (B) is a compound selected from: fluopyram, benzovindiflupyr, azoxystrobin, pyridaben, difenoconazole, prothioconazole, chlorfluazuron, pyrimethanil, fludioxonil, aramid-type benzyl-S-methyl, N-[(1R)-1-benzyl-1,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide, N-[(1S)-1-benzyl-1,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide, 2-[cyano-(2,6-difluoro-4-pyridyl)amino]-5-methyl-N-spiro[3,4]oct-3-yl-thiazolyl-4-carboxamide, 2-[cyano-(2,6-difluoro-4-pyridyl)amino]-5-methyl-N-spiro[3,4]oct-3-yl-thiazolyl-4-carboxamide, 2-[cyano-(2,6-difluoro-4-pyridyl)amino]-5-methyl-N-spiro[3,4]oct-3-yl-thiazolyl-4-carboxamide, [Fluoro-4-pyridinyl)amino]-N-(2,2-dimethylcyclobutyl)-5-methyl-thiazole-4-carboxamide, 2-[(2,6-difluoro-4-pyridinyl)-(tetrahydropyran-4-carbonyl)amino]-N-(2,2-dimethylcyclobutyl)-5-methyl-thiazole-4-carboxamide, 2-[acetyl-(2,6-difluoro-4-pyridinyl)amino]-N-(2,2-dimethylcyclobutyl)-5-methyl-thiazole-4-carboxamide, TAEGRO® (i.e., Bacillus amyloliquefaciens strain FZB24), Melaleuca alternifolia oil (Melaleuca alternifolia extract from the tea plant (commercially available as Timorx Gold®, a broad-spectrum phytofungicide)), Polygonum cuspidatum extract (commercially available as REGALIA®), plant extracts based on Alternaria solani extract (commercially available as BOTRISTOP®), or basidiosin A.

7. The antifungal composition according to any one of claims 1 to 6, wherein component (B) is a compound selected from: fluopyram, benzovindiflupyr, azoxystrobin, pyridaben, difenoconazole, prothioconazole, chlorfluazuron, azoxystrobin, fludioxonil, or aramid-type benzene-S-methyl.

8. The antifungal composition according to any one of claims 1 to 7, wherein the weight ratio of component (A) to component (B) is from 20:1 to 1:40.

9. The antifungal composition according to any one of claims 1 to 8, wherein the weight ratio of component (A) to component (B) is from 12:1 to 1:25.

10. The antifungal composition according to any one of claims 1 to 9, wherein the weight ratio of component (A) to component (B) is from 5:1 to 1:15.

11. The antifungal composition according to any one of claims 1 to 10, wherein the weight ratio of component (A) to component (B) is from 2:1 to 1:5.

12. The fungicidal composition according to any one of claims 1 to 11, wherein the composition comprises one or more additional pest control agents selected from the group consisting of: fluopyram, benzovindiflupyr, bifenthiophanate-methyl, fluopyram, pyraclostrobin, fluopyram, pyraclostrobin, pyraclostrobin, fluopyram, fluopyram, thiamethoxam, bifenthiamethoxam, isopropoxypyram, indapoxam, isopropoxypyram, fluopyram, triflupyridam, flupyraclostrobin, imidacloprid, toluenefloxacin, pyridoxam, pyraclostrobin Oxadiazon, Azoxystrobin-methyl, Azoxystrobin, Pyrimethanil, Tetracycline, Indazole, Cyazofamid, Pyridaben, Pyridabenamide, Pyridabenamide, Azoxystrobin, Fluazinam, Triphenyltin hydroxide, Silthiamethoxam, Butylmorpholine, Benzoyl, Spirocyclohexane, Cyclopyralid, Imazalil, Pyrimethanil, Fenoxacillin, Cyclopyralid, Difenoconazole, Fluconazole, Tebuconazole, Hexaconazole, Izoxystrobin, Imidacloprid, Cyclopyralid, Tebuconazole, Fluazinam, Mefenoxam, Prothioconazole, Fluopyram, Chlorothalonil, Fluazinam, Isopropylquinoline, Fluazinam Quinoline, Metalaxyl-M, Azoxystrobin, Pyrimethanil, Kasugamycin, Mancozeb, Copper Fungicide, Sulfur, Thiazole Zinc, Captan, Mancozeb, Chlorothalonil, Dithiamethoxam, Quinoxazone, Propoxyquin, Fludioxonil, Iprodione, Iprodione, Thibendazole, Benzoylamidone, Benomyl, Fluopyram, Cymoxanil, Fluoxadiazon, Aramaic acid benzyl-S-methyl, Isothiazamine, Phosphorous acid, Cyclofluopyram, Isobutylethoxyquinoline, Tetracycline, Tricyclazole, N-Methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazole-3 [-yl]phenyl]methyl]cyclopropane-formamide, N,2-dimethoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propamide, N-[(1R)-1-benzyl-1,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide, N-[(1S)-1-benzyl-1,3-dimethyl-butyl]-8-fluoro-quinoline-3-carboxamide, (Z)-2-(5-cyclohexyl-2-methyl-phenoxy)-3-methoxy-prop-2-enoic acid methyl ester (this compound can be derived from WO Prepared by the method described in 2020/193387), 2-[cyano-(2,6-difluoro-4-pyridinyl)amino]-5-methyl-N-spiro[3,4]oct-3-yl-thiazolyl-4-carboxamide, 2-[cyano-(2,6-difluoro-4-pyridinyl)amino]-N-(2,2-dimethylcyclobutyl)-5-methyl-thiazolyl-4-carboxamide, 2-[(2,6-di-... [Fluoro-4-pyridyl)-(2-methoxyacetyl)amino]-N-(2,2-dimethylcyclobutyl)-5-methyl-thiazol-4-carboxamide, 2-[(2,6-difluoro-4-pyridyl)-(tetrahydropyran-4-carbonyl)amino]-N-(2,2-dimethylcyclobutyl)-5-methyl-thiazol-4-carboxamide, 2-[(2,6-difluoro-4-pyridyl)-(oxocyclic) [Butane-3-carbonyl)amino]-N-(2,2-dimethylcyclobutyl)-5-methyl-thiazole-4-carboxamide, 2-[(2,6-difluoro-4-pyridyl)-(tetrahydrofuran-3-carbonyl)amino]-N-(2,2-dimethylcyclobutyl)-5-methyl-thiazole-4-carboxamide, 2-[acetyl-(2,6-difluoro-4-pyridyl)amino]-N-(2,2-dimethylcyclobutyl)-5-methyl-thiazole-4-carboxamide, 2-[(2,6-difluoro-4-pyridyl)-(2-methylpropionyl)amino]-N-(2,2-dimethylcyclobutyl)-5-methyl-thiazole-4-carboxamide, TAEGRO® (Bacillus amyloliquefaciens strain FZB24), Melaleuca alternifolia oil (tea tree plant Melaleuca alternifolia extract (as Timorex) Gold® (available commercially, as a broad-spectrum plant-based fungicide), Polygonum cuspidatum extract (available commercially as REGALIA®), a plant extract based on Alpinia serratifolia extract (available commercially as BOTRISTOP®), or gold basidiosin A.

13. The fungicidal composition according to any one of claims 1 to 12, wherein the composition further comprises an agriculturally acceptable carrier and optionally a surfactant and/or formulation adjuvant.

14. A method for controlling or preventing plant pathogenic diseases, particularly plant pathogenic fungi, on useful plants or their propagation material, the method comprising applying a fungicidal composition comprising component (A) and component (B) as described in any one of claims 1 to 12 to said useful plant, its location, or its propagation material.

15. The method of claim 14, wherein the components (A) and (B) are applied in a sequential manner.