Substituted thiophenecarboxamides, thiophenecarboxylic acids and their derivatives

Abstract

The present disclosure relates to substituted thiophenecarboxamide derivatives of formula (I) and (II), their use for controlling phytopathogenic microorganisms, and compositions comprising them.

Description

Technical Field

[0001] The present invention relates to substituted thiophenecarboxamide derivatives, their use for controlling phytopathogenic microorganisms, and compositions comprising them. Background Art

[0002] Although many microbicides have been developed to date, there is still a need to develop new microbicidal compounds to meet the increasing environmental and economic requirements imposed on modern crop protection agents and compositions. For example, this includes improving the spectrum of action, safety, selectivity, application rate, formation of residues, and favorable preparation capabilities. There may also be a need for new compounds to prevent the emergence of resistance.

[0003] The present invention provides new compounds that are superior to known compounds and compositions in at least some of these aspects.

[0004] EP 450355 and JP 2009078991 disclose thiophenecarboxamide derivatives that can be used to protect plants against attack by phytopathogenic microorganisms.

[0005] WO 2004 / 024692 discloses heterocyclic carboxylic acid derivatives and their use as fungicides and bactericides for protecting plants or materials such as wood. Summary of the Invention

[0006] The present invention relates to compounds of formula (I) and formula (II) as described herein, and their isomers, polymorphs, salts, N-oxides, and solvates.

[0007] The present invention relates to compositions comprising at least one compound of formula (I) or formula (II) as defined herein and at least one agriculturally suitable carrier.

[0008] The present invention relates to methods for preparing compounds of formula (I) or formula (II) as described herein and their intermediates.

[0009] The present invention relates to a method for controlling phytopathogenic microorganisms, which comprises the step of applying at least one compound of formula (I) or formula (II) as defined herein or a composition as defined herein to plants, plant parts, seeds, fruits, or the soil in which plants grow.

[0010] Definitions

[0011] The term "alkyl" as used herein, for example, in the context of alkyl or alkylsulfonyl, alkylsulfinyl, alkylthio, alkylamino, is preferably understood to mean branched and unbranched alkyl, meaning, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, pentyl, isopentyl, hexyl, heptyl, octyl, nonyl, and decyl and their isomers.

[0012] As used herein, the term "alkenyl" is preferably understood to mean branched and unbranched alkenyls, such as vinyl, prop-1-en-1-yl, prop-2-en-1-yl, but-1-en-1-yl, but-1-en-2-yl, but-2-en-1-yl, but-2-en-2-yl, but-1-en-3-yl, 2-methyl-prop-2-en-1-yl or 2-methyl-prop-1-en-1-yl.

[0013] As used herein, the term "alkynyl" is preferably understood to mean branched and unbranched alkynyls, such as ethynyl, prop-1-yn-1-yl, but-1-yn-1-yl, but-2-yn-1-yl or but-3-yn-1-yl.

[0014] As used herein, the term "halogen" or "Hal" is understood to mean fluorine, chlorine, bromine or iodine.

[0015] The term "halo" or "halogeno" (e.g., haloalkyl, "C1-C6-haloalkyl" or "C1-C8-haloalkyl") means that one or more halogen substituents may optionally be present, which may be the same or different.

[0016] As used herein, the term "haloalkyl" is preferably understood to mean branched and unbranched alkyls as defined above, wherein one or more hydrogen substituents are replaced by halogen in the same or different manner. Particularly preferably, the haloalkyl is, for example, chloromethyl, fluoropropyl, fluoromethyl, difluoromethyl, trichloromethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, bromobutyl, trifluoromethyl, iodoethyl and its isomers.

[0017] As used herein, the term "haloalkenyl" is preferably understood to mean branched and unbranched alkenyls as defined above, wherein one or more hydrogen substituents are replaced by halogen in the same or different manner.

[0018] As used herein, the term "haloalkynyl" is preferably understood to mean branched and unbranched alkynyls as defined above, wherein one or more hydrogen substituents are replaced by halogen in the same or different manner.

[0019] As used herein, the term "alkoxy" refers to a group of the formula (alkyl)-O-, where the term "alkyl" is as defined herein. Examples of C1-C8-alkoxy include, but are not limited to, methoxy, ethoxy, n-propoxy, 1-methylethoxy, n-butoxy, 1-methylpropoxy, 2-methylpropoxy, 1,1-dimethylethoxy, n-pentyloxy, 1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 2,2-dimethylpropoxy, 1-ethylpropoxy, 1,1-dimethylpropoxy, 1,2-dimethylpropoxy, n-hexyloxy, 1-methylpentyloxy, 2-methylpentyloxy, 3-methylpentyloxy, 4-methylpentyloxy, 1,1-dimethylbutoxy, 1,2-dimethylbutoxy, 1,3-dimethylbutoxy, 2,2-dimethylbutoxy, 2,3-dimethylbutoxy, 3,3-dimethylbutoxy, 1-ethylbutoxy, 2-ethylbutoxy, 1,1,2-trimethylpropoxy, 1,2,2-trimethylpropoxy, 1-ethyl-1-methylpropoxy and 1-ethyl-2-methylpropoxy.

[0020] As used herein, the term "haloalkoxy" refers to an alkoxy as defined above, where one or more hydrogen atoms are replaced by one or more halogen atoms which may be the same or different. Examples of C1-C8-haloalkoxy include, but are not limited to, chloromethoxy, bromomethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 1-chloroethoxy, 1-bromoethoxy, 1-fluoroethoxy, 2-fluoroethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2-trichloroethoxy, pentafluoroethoxy and 1,1,1-trifluoropropan-2-oxy.

[0021] As used herein, the term "alkylthio" refers to a saturated, straight-chain or branched-chain group of the formula (alkyl)-S-, where the term "alkyl" is as defined herein. Examples of C1-C8-alkylthio include, but are not limited to, methylthio, ethylthio, propylthio, isopropylthio, butylthio, sec-butylthio, isobutylthio, tert-butylthio, pentylthio, isopentylthio, hexylthio.

[0022] As used herein, the term "haloalkylthio" refers to an alkylthio as defined above, where one or more hydrogen atoms are replaced by one or more halogen atoms which may be the same or different.

[0023] As used herein, the term "alkylsulfinyl" refers to a saturated, straight-chain or branched-chain group of the formula (alkyl)-S(=O)-, where the term "alkyl" is as defined herein. Examples of C1-C8-alkylsulfinyl include, but are not limited to, saturated straight-chain or branched-chain alkylsulfinyl groups having from 1 to 8, preferably from 1 to 6, more preferably from 1 to 4 carbon atoms, such as (but not limited to) methylsulfinyl, ethylsulfinyl, propylsulfinyl, 1-methylpropylsulfinyl, butylsulfinyl, 1-methylpropylsulfinyl, 2-methylpropylsulfinyl, 1,1-dimethylpropylsulfinyl, pentylsulfinyl, 1-methylbutylsulfinyl, 2-methylbutylsulfinyl, 3-methylbutylsulfinyl, 2,2-dimethylpropylsulfinyl, 1-ethylpropylsulfinyl, 1,1-dimethylpropylsulfinyl, 1,2-dimethylpropylsulfinyl, hexylsulfinyl, 1-methylpentylsulfinyl, 2-methylpentylsulfinyl, 3-methylpentylsulfinyl, 4-methylpentylsulfinyl, 1,1-dimethylbutylsulfinyl, 1,2-dimethylbutylsulfinyl, 1,3-dimethylbutylsulfinyl, 2,2-dimethylbutylsulfinyl, 2,3-dimethylbutylsulfinyl, 3,3-dimethylbutylsulfinyl, 1-ethylbutylsulfinyl, 2-ethylbutylsulfinyl, 1,1,2-trimethylpropylsulfinyl, 1,2,2-trimethylpropylsulfinyl, 1-ethyl-1-methylpropylsulfinyl, and 1-ethyl-2-methylpropylsulfinyl.

[0024] As used herein, the term "haloalkylsulfinyl" refers to an alkylsulfinyl group as defined above, where one or more hydrogen atoms are replaced by one or more halogen atoms which may be the same or different.

[0025] As used herein, the term "alkylsulfonyl" refers to a saturated straight-chain or branched-chain group of the formula (alkyl)-S(=O)2-, where the term "alkyl" is as defined herein. Examples of C1-C8-alkylsulfonyl include, but are not limited to, methylsulfonyl, ethylsulfonyl, propylsulfonyl, 1-methylethylsulfonyl, butylsulfonyl, 1-methylpropylsulfonyl, 2-methylpropylsulfonyl, 1,1-dimethylethylsulfonyl, pentylsulfonyl, 1-methylbutylsulfonyl, 2-methylbutylsulfonyl, 3-methylbutylsulfonyl, 2,2-dimethylpropylsulfonyl, 1-ethylpropylsulfonyl, 1,1-dimethylpropylsulfonyl, 1,2-dimethylpropylsulfonyl, hexylsulfonyl, 1-methylpentylsulfonyl, 2-methylpentylsulfonyl, 3-methylpentylsulfonyl, 4-methylpentylsulfonyl, 1,1-dimethylbutylsulfonyl, 1,2-dimethylbutylsulfonyl, 1,3-dimethylbutylsulfonyl, 2,2-dimethylbutylsulfonyl, 2,3-dimethylbutylsulfonyl, 3,3-dimethylbutylsulfonyl, 1-ethylbutylsulfonyl, 2-ethylbutylsulfonyl, 1,1,2-trimethylpropylsulfonyl, 1,2,2-trimethylpropylsulfonyl, 1-ethyl-1-methylpropylsulfonyl, and 1-ethyl-2-methylpropylsulfonyl.

[0026] As used herein, the term "haloalkylsulfonyl" refers to a C1-C8-alkylsulfonyl as defined above, where one or more hydrogen atoms are replaced by one or more halogen atoms which may be the same or different.

[0027] As used herein, the term "alkylcarbonyl" refers to a saturated, straight-chain or branched-chain group of the formula (alkyl)-C(=O)-, where the term "alkyl" is as defined herein.

[0028] As used herein, the term "haloalkylcarbonyl" refers to an alkylcarbonyl as defined above, where one or more hydrogen atoms are replaced by one or more halogen atoms which may be the same or different.

[0029] As used herein, the term "alkoxycarbonyl" refers to a saturated straight-chain or branched-chain group of the formula (alkoxy)-C(=O)-, where the term "alkoxy" is as defined herein.

[0030] As used herein, the term "haloalkoxycarbonyl" refers to an alkoxycarbonyl as defined above, where one or more hydrogen atoms are replaced by one or more halogen atoms which may be the same or different.

[0031] As used herein, the term "cycloalkyl" refers to a non-aromatic monocyclic carbon ring having 3 to 8 carbon atoms. Examples of saturated cycloalkyl include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl.

[0032] As used herein, the term "heterocyclic group" refers to a four-, five- or six-membered saturated or partially unsaturated heterocycle containing one to four heteroatoms independently selected from oxygen, nitrogen and sulfur. If the ring contains more than one oxygen atom, they are not directly adjacent.

[0033] As used herein, the term "aryl" refers to an aromatic hydrocarbon ring system containing 6 to 15 carbon atoms, or 6 to 12 carbon atoms, preferably 6 to 10 carbon atoms. The ring system can be a monocyclic or fused polycyclic (e.g., bicyclic or tricyclic) aromatic ring system. Examples of aryl include, but are not limited to, phenyl, azulenyl, naphthyl and fluorenyl. It should also be understood that when the aryl is substituted with one or more substituents, the one or more substituents can be located at any position on the aryl ring. In particular, when the aryl is phenyl, the one or more substituents can occupy one or two ortho positions, one or two meta positions, or the para position, or any combination of these positions. This definition also applies to aryl as part of a complex substituent (e.g., aryloxy).

[0034] As used herein, the term "aralkyl" refers to a C1-C6-alkyl substituted with an aryl as defined herein. Examples of aralkyl include benzyl (-CH2-C6H5).

[0035] As used herein, the term "aromatic 5- to 14-membered heterocycle" or "heteroaryl" refers to an aromatic ring system containing 1 to 4 heteroatoms independently selected from oxygen, nitrogen and sulfur. Aromatic heterocycles include aromatic 5- or 6-membered monocyclic heterocycles and 6- to 14-membered polycyclic (e.g., bicyclic or tricyclic) aromatic heterocycles. The 5- to 14-membered aromatic heterocycle can be attached to the parent molecular moiety through any carbon or nitrogen atom contained in the heterocycle.

[0036] As used herein, the term "C1-C6", for example in the context of the definition of "C1-C6 alkyl" or "C1-C6 alkoxy", should be understood to mean a group having a limited number of carbon atoms from 1 to 6 (i.e., 1, 2, 3, 4, 5 or 6 carbon atoms).

[0037] As used herein, the term "C1-C8", for example in the context of the definition of "C1-C8-alkyl" or "C1-C8-alkoxy", should be understood to mean a group having a limited number of carbon atoms from 1 to 8 (i.e., 1, 2, 3, 4, 5, 6, 7 or 8).

[0038] As used herein, the term "oxo" refers to an oxygen atom bonded to a carbon or sulfur atom by a double bond.

[0039] As used herein, the term "leaving group" should be understood to mean a group displaced from a compound in a substitution or elimination reaction, such as a halogen atom, a trifluoromethanesulfonate ("triflate") group, an alkoxy group, a methanesulfonate, a p-toluenesulfonate, etc. Detailed implementation mode

[0040] The present invention relates to compounds of formula (I),

[0041]

[0042] wherein

[0043] R 1 and R 2 are each independently selected from halogen, cyano, C1-C6-alkyl or C1-C6-haloalkyl, wherein R 1 or R 2 at least one of which is halogen;

[0044] R 3 is selected from hydrogen, halogen, cyano, C1-C6-alkyl or C1-C6-haloalkyl;

[0045] R 4 and R 5Independently of one another, selected from: hydrogen; halogen; cyano; hydroxy; C1-C6-alkyl; C1-C6-hydroxyalkyl; C1-C6-alkoxy; C1-C6-haloalkyl; -O-C(=O)-C1-C6-alkyl; C3-C6-carbocycle; 4-, 5- or 6-membered non-aromatic heterocyclic group; -C(=O)-NH2, -C(=O)-NH(C1-C6-alkyl), -C(=O)-N(C1-C6-alkyl)2, -C(=O)-OH, -C(=O)-O-C1-C6-alkyl, aryl, 5- or 9-membered heteroaryl, -C1-C6-alkyl-C1-C6-alkoxy, -C1-C6-alkyl-C1-C6-haloalkyl, -C1-C6-alkyl-C3-C6-carbocycle; -C1-C6-alkyl-4-, 5- or 6-membered non-aromatic heterocyclic group, -C1-C6-alkyl-aryl, -C1-C6-alkyl-hydroxyaryl, -C1-C6-alkyl-5- to 9-membered heteroaryl, -C1-C6-alkyl-S-C1-C6-alkyl, -C1-C6-alkyl-S-C(=O)-C1-C6-alkyl, -C1-C6-alkyl-O-(C=O)-C1-C6-alkyl, -C1-C6-alkyl-C(=O)-NH2, -C1-C6-alkyl-C(=O)-NH(C1-C6-alkyl), -C1-C6-alkyl-C(=O)-N(C1-C6-alkyl)2, -C1-C6-alkyl-C(=O)-OH, -C1-C6-alkyl-C(=O)-O-C1-C6-alkyl, -C1-C6-alkyl-NH-C(=NH)-NH2, -S-C1-C6-alkyl, -S-C(=O)-C1-C6-alkyl, -S-C(=O)-O-C1-C6-alkyl, -S-C(=S)-O-C1-C6-alkyl, -S-C(=O)-S-C1-C6-alkyl, -S-C(=O)-NH2, -S-C(=O)-NH(C1-C6-alkyl), -S-C(=O)-NH(C1-C6-alkyl)2, -S-C(=S)-NH2, -S-C(=S)-NH(C1-C6-alkyl), -S-C(=S)-NH(C1-C6-alkyl)2, -C1-C6-alkyl-S-C(=O)-O-C1-C6-alkyl, -C1-C6-alkyl-S-C(=O)-S-C1-C6-alkyl, -C1-C6-alkyl-S-C(=O)-NH2, -C1-C6-alkyl-S-C(=O)-NH(C1-C6-alkyl), -C1-C6-alkyl-S-C(=O)-NH(C1-C6-alkyl)2, -C1-C6-alkyl-S-C(=S)-NH2, -C1-C6-alkyl-S-C(=S)-NH(C1-C6-alkyl), -C1-C6-alkyl-S-C(=S)-NH(C1-C6-alkyl)2, wherein acyclic R 4, R 5 The group can be substituted by one or more R w substituents, wherein the cyclic R 4 , R 5 The group can be substituted by one or more R x substituents, wherein at least one of R 4 and R 5 is hydrogen, C1-C6-alkyl or C3-C6-cycloalkyl, or R 4 and R 5 together with the carbon atom to which they are attached form a C3-C6-cycloalkyl or a 3- to 6-membered heterocycle, wherein the C3-C6-cycloalkyl and the 3- to 6-membered heterocycle can be substituted by one or more R x substituents, wherein R w is independently selected from nitro, hydroxy, cyano, carboxy, amino, thioalkyl, pentafluoro-λ 6 -thioalkyl, formyl, carbamoyl, carbamate, C3-C7-cycloalkyl, C3-C7-halocycloalkyl having 1 to 5 halogen atoms, C1-C8-alkylamino, di-C1-C8-alkylamino, C1-C8-alkoxy, C1-C8-haloalkoxy having 1 to 5 halogen atoms, C1-C8-alkylthio, C1-C8-haloalkylthio having 1 to 5 halogen atoms, C1-C8-alkylcarbonyl, C1-C8-haloalkylcarbonyl having 1 to 5 halogen atoms, C1-C8-alkylcarbamoyl, di-C1-C8-alkylcarbamoyl, C1-C8-alkoxycarbonyl, C1-C8-haloalkoxycarbonyl having 1 to 5 halogen atoms, C1-C8-alkylcarbonyloxy, C1-C8-haloalkylcarbonyloxy having 1 to 5 halogen atoms, C1-C8-alkylcarbonylamino, C1-C8-haloalkylcarbonylamino having 1 to 5 halogen atoms, C1-C8-alkylsulfinyl, C1-C8-haloalkylsulfinyl having 1 to 5 halogen atoms, C1-C8-alkylsulfonyl, C1-C8-haloalkylsulfonyl having 1 to 5 halogen atoms; C1-C8-alkylsulfonylamino, C1-C8-haloalkylsulfonylamino having 1 to 5 halogen atoms; sulfamoyl; C1-C8-alkylsulfamoyl and di-C1-C8-alkylsulfamoyl, wherein R x is independently selected from halogen, nitro, hydroxy, cyano, carbonyl, amino, thioalkyl, pentafluoro-λ 6-thioalkyl, formyl, carbamoyl, carbamate, C1-C8-alkyl, C3-C7-cycloalkyl, C1-C8-haloalkyl having 1 to 5 halogen atoms, C3-C7-halocycloalkyl having 1 to 5 halogen atoms, C2-C8-alkenyl, C2-C8-alkynyl, C1-C8-alkylamino, di-C1-C8-alkylamino, C1-C8-alkoxy, C1-C8-haloalkoxy having 1 to 5 halogen atoms, C1-C8-alkylthio, C1-C8-haloalkylthio having 1 to 5 halogen atoms, C1-C8-alkylcarbonyl, C1-C8-haloalkylcarbonyl having 1 to 5 halogen atoms, C1-C8-alkylcarbamoyl, di-C1-C8-alkylcarbamoyl, C1-C8-alkoxycarbonyl, C1-C8-haloalkoxycarbonyl having 1 to 5 halogen atoms, C1-C8-alkylcarbonyloxy, C1-C8-haloalkylcarbonyloxy having 1 to 5 halogen atoms, C1-C8-alkylcarbonylamino, C1-C8-haloalkylcarbonylamino having 1 to 5 halogen atoms, C1-C8-alkylthio, C1-C8-haloalkylthio having 1 to 5 halogen atoms, C1-C8-alkylsulfinyl, C1-C8-haloalkylsulfinyl having 1 to 5 halogen atoms, C1-C8-alkylsulfonyl, C1-C8-haloalkylsulfonyl having 1 to 5 halogen atoms; C1-C8-alkylsulfonylamino, C1-C8-haloalkylsulfonylamino having 1 to 5 halogen atoms; sulfamoyl; C1-C8-alkylsulfamoyl and di-C1-C8-alkylsulfamoyl;

[0046] R 6 and R 7 are independently selected from hydrogen, C1-C6-alkyl, C3-C6-carbocyclic ring, or R 6 and R 7 together with the carbon atom to which they are attached form a C3-C6-carbocyclic ring or a 3- to 6-membered heterocyclic ring;

[0047] n is 0 or 1;

[0048] W is oxygen or sulfur;

[0049] Y is NR 8 wherein R 8 is selected from hydrogen, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-cyanoalkyl, hydroxy, C1-C6-alkoxy or C3-C6-carbocyclic ring;

[0050] Z is selected from cyano, -C(=O)-OR a 、-C(=O)-SR a 、-C(=O)-NR b R c 、-C(=S)-NRb R c

[0051] or -C(=O)-NH-CR d R e -C(=O)-OR a , wherein R a is selected from hydrogen; C1-C6-alkyl; C1-C6-haloalkyl; C1-C6-cyanoalkyl; C2-C6-alkenyl, C2-C6-alkynyl; C3-C8-cycloalkyl; aryl; aralkyl; 4-, 5- or 6-membered non-aromatic heterocyclic group; -C1-C6-alkyl-Si(C1-C6-alkyl)3; -C1-C6-alkyl-C3-C8-cycloalkyl; 5- to 9-membered heteroaryl and -C1-C6-alkyl-5- to 9-membered heteroaryl, or R a may together with R 4 and the atoms to which they are attached form a 4- to 7-membered heterocycle, wherein R b and R c are independently selected from hydrogen, C1-C6-alkyl, hydroxy, C1-C6-alkoxy, cyano, C1-C6-cyanoalkyl, or R b may together with R 4 and the atoms to which they are attached form a 4- to 7-membered heterocycle, wherein R d and R e are independently selected from hydrogen, cyano, hydroxy, C1-C6-alkyl, C1-C6-hydroxyalkyl, C1-C6-alkoxy, -O-C(=O)-C1-C6-alkyl, C3-C6-carbocycle, -C(=O)-NH2, -C(=O)-NH(C1-C6-alkyl)-, C(=O)-N(C1-C6-alkyl)2, -C(=O)-OH, -C(=O)-O-C1-C6-alkyl, aryl, 5- to 9-membered heteroaryl, -C1-C6-alkyl-C1-C6-alkoxy, -C1-C6-alkyl-C3-C6-carbocycle, -C1-C6-alkyl-aryl, -C1-C6-alkyl-hydroxyaryl, -C1-C6-alkyl-5- to 9-membered heteroaryl, -C1-C6-alkyl-S-C1-C6-alkyl, -C1-C6-alkyl-S-C(=O)-C1-C6-alkyl, -C1-C6-alkyl-O-(C=O)-C1-C6-alkyl, -C1-C6-alkyl-C(=O)-NH2, -C1-C6-alkyl-C(=O)-NH(C1-C6-alkyl)-, -C1-C6-alkyl-C(=O)-N(C1-C6-alkyl)2, -C1-C6-alkyl-C(=O)-OH, -C1-C6-alkyl-C(=O)-O-C1-C6-alkyl, -C1-C6-alkyl-NH-C(=NH)-NH2, wherein R d and R eat least one of which is hydrogen, C1-C6-alkyl or C3-C6-cycloalkyl, or R d and R e together with the carbon atom to which they are attached form a carbonyl group, a C3-C6-cycloalkyl or a 3- to 6-membered heterocycle;

[0052] provided that compounds of formula (I) having the following combinations of R 1 , R 2 and R 3 are excluded

[0053] <![CDATA[R 1 > <![CDATA[R 2 > <![CDATA[R 3 > Cl Cl Cl Br Me H Br Br Br Cl Cl Methyl Br Br Methyl Br Br H Cl Cl H

[0054] provided that, if R 4 and R 5 together with the carbon atom to which they are attached form cyclopropyl, and n is 0, W is oxygen, Y is NH, and Z is -C(=O)-OR a , then compounds of formula (I) having the following combinations of R 1 , R 2 and R 3 are excluded

[0055] <![CDATA[R 1 > <![CDATA[R 2 > <![CDATA[R 3 > Cl Cl Halogen Br Br Halogen

[0056] provided that, if R 4 is selected from hydrogen, C1-C6-alkyl, -C1-C6-alkyl-aryl, -C1-C6-alkyl-hydroxyaryl, -C1-C6-alkyl-S-C1-C6-alkyl, and R 5 is hydrogen, n is 0, W is oxygen, Y is NH, and Z is -C(=O)-OR a , then compounds of formula (I) having the following combinations of R 1 , R 2 and R 3 are excluded

[0057] <![CDATA[R 1 > <![CDATA[R 2 > <![CDATA[R 3 > Cl Cl Br Cl Cl I Br Br I

[0058] provided that N-[(4-bromo-5-methyl-2-thienyl)carbonyl]-N-propylglycine [2193740-02-0] and 4-bromo-N-(1-cyano-2,2-dimethylcyclopropyl)-5-methylthiophene-2-carboxamide [2192630-99-0] are excluded from the compounds of formula (I).

[0059] Preferably if R 1 is C1-C6-haloalkyl or R 2 is C1-C6-haloalkyl and R 4 is selected from hydrogen, C1-C6-alkyl and R 5Selected from hydrogen, C1-C6-alkyl, n is 0, W is oxygen, then Z is selected from cyano, -C(=O)-SR a 、-C(=O)-NR b R c 、-C(=S)-NR b R c or -C(=O)-NH-CR d R e -C(=O)-OR a 。

[0060] Also preferably does not include compounds of formula (I) wherein R 1 、R 2 and R 3 are independently selected from halogen and C1-C6-alkyl; W is oxygen; Y is NH; R 4 and R 5 together with the carbon atom to which they are attached form cyclopropyl; n is 0; Z is selected from -C(=O)-OR a 、-C(=O)-NR b R c 。

[0061] R 4 and R 5Each is independently preferably selected from: hydrogen; halogen; cyano; hydroxy; C1-C6-alkyl, C1-C6-hydroxyalkyl; C1-C6-alkoxy; C1-C6-haloalkyl; -O-C(=O)-C1-C6-alkyl; C3-C6-carbocycle; 4-, 5- or 6-membered non-aromatic heterocyclic group; -C(=O)-NH2; -C(=O)-NH(C1-C6-alkyl); -C(=O)-N(C1-C6-alkyl)2; -C(=O)-OH; -C(=O)-O-C1-C6-alkyl; aryl; 5- to 9-membered heteroaryl; -C1-C6-alkyl-C1-C6-alkoxy; -C1-C6-alkyl-C1-C6-haloalkyl; -C1-C6-alkyl-C3-C6-carbocycle; -C1-C6-alkyl-4-, 5- or 6-membered non-aromatic heterocyclic group; -C1-C6-alkyl-aryl; -C1-C6-alkyl-hydroxyaryl; -C1-C6-alkyl-5- to 9-membered heteroaryl; -C1-C6-alkyl-S-C1-C6-alkyl; -C1-C6-alkyl-S-C(=O)-C1-C6-alkyl; -C1-C6-alkyl-O-(C=O)-C1-C6-alkyl; -C1-C6-alkyl-C(=O)-NH2; -C1-C6-alkyl-C(=O)-NH(C1-C6-alkyl); -C1-C6-alkyl-C(=O)-N(C1-C6-alkyl)2; -C1-C6-alkyl-C(=O)-OH; -C1-C6-alkyl-C(=O)-O-C1-C6-alkyl; -C1-C6-alkyl-NH-C(=NH)-NH2; -S-C1-C6-alkyl; -S-C(=O)-C1-C6-alkyl; -S-C(=O)-O-C1-C6-alkyl; -S-C(=S)-O-C1-C6-alkyl; -S-C(=O)-S-C1-C6-alkyl; -S-C(=O)-NH2; -S-C(=O)-NH(C1-C6-alkyl); -S-C(=O)-NH(C1-C6-alkyl)2; -S-C(=S)-NH2; -S-C(=S)-NH(C1-C6-alkyl); -S-C(=S)-NH(C1-C6-alkyl)2; -C1-C6-alkyl-S-C(=O)-O-C1-C6-alkyl; -C1-C6-alkyl-S-C(=O)-S-C1-C6-alkyl; -C1-C6-alkyl-S-C(=O)-NH2; -C1-C6-alkyl-S-C(=O)-NH(C1-C6-alkyl); -C1-C6-alkyl-S-C(=O)-NH(C1-C6-alkyl)2; -C1-C6-alkyl-S-C(=S)-NH2; -C1-C6-alkyl-S-C(=S)-NH(C1-C6-alkyl); -C1-C6-alkyl-S-C(=S)-NH(C1-C6-alkyl)2, wherein acyclic R 4, R 5 The group may be substituted by one or more R w substituents, wherein the cyclic R 4 , R 5 group may be substituted by one or more R x substituents, wherein at least one of R 4 and R 5 is hydrogen, C1-C6-alkyl or C3-C6-cycloalkyl, or R 4 and R 5 together with the carbon atom to which they are attached form a C4-C6-cycloalkyl or a 3- to 6-membered heterocyclic ring, wherein the C4-C6-cycloalkyl and the 3- to 6-membered heterocyclic ring may be substituted by one or more R x substituents, wherein R w is independently selected from: nitro, hydroxy, cyano, carboxy, amino, thioalkyl, pentafluoro-λ 6 -thioalkyl, formyl, carbamoyl, carbamate, C3-C7-cycloalkyl, C3-C7-halocycloalkyl having 1 to 5 halogen atoms, C1-C8-alkylamino, di-C1-C8-alkylamino, C1-C8-alkoxy, C1-C8-haloalkoxy having 1 to 5 halogen atoms, C1-C8-alkylthio, C1-C8-haloalkylthio having 1 to 5 halogen atoms, C1-C8-alkylcarbonyl, C1-C8-haloalkylcarbonyl having 1 to 5 halogen atoms, C1-C8-alkylcarbamoyl, di-C1-C8-alkylcarbamoyl, C1-C8-alkoxycarbonyl, C1-C8-haloalkoxycarbonyl having 1 to 5 halogen atoms, C1-C8-alkylcarbonyloxy, C1-C8-haloalkylcarbonyloxy having 1 to 5 halogen atoms, C1-C8-alkylcarbonylamino, C1-C8-haloalkylcarbonylamino having 1 to 5 halogen atoms, C1-C8-alkylsulfinyl, C1-C8-haloalkylsulfinyl having 1 to 5 halogen atoms, C1-C8-alkylsulfonyl, C1-C8-haloalkylsulfonyl having 1 to 5 halogen atoms, C1-C8-alkylsulfonylamino, C1-C8-haloalkylsulfonylamino having 1 to 5 halogen atoms, sulfamoyl, C1-C8-alkylsulfamoyl and di-C1-C8-alkylsulfamoyl, wherein R x is independently selected from halogen nitro, hydroxy, cyano, carboxy, amino, thioalkyl, pentafluoro-λ 6-thioalkyl, formyl, carbamoyl, carbamate, C1-C8-alkyl, C3-C7-cycloalkyl, C1-C8-haloalkyl having from 1 to 5 halogen atoms, C3-C7-halocycloalkyl having from 1 to 5 halogen atoms, C2-C8-alkenyl, C2-C8-alkynyl, C1-C8-alkylamino, di-C1-C8-alkylamino, C1-C8-alkoxy, C1-C8-haloalkoxy having from 1 to 5 halogen atoms, C1-C8-alkylthio, C1-C8-haloalkylthio having from 1 to 5 halogen atoms, C1-C8-alkylcarbonyl, C1-C8-haloalkylcarbonyl having from 1 to 5 halogen atoms, C1-C8-alkylcarbamoyl, di-C1-C8-alkylcarbamoyl, C1-C8-alkoxycarbonyl, C1-C8-haloalkoxycarbonyl having from 1 to 5 halogen atoms, C1-C8-alkylcarbonyloxy, C1-C8-haloalkylcarbonyloxy having from 1 to 5 halogen atoms, C1-C8-alkylcarbonylamino, C1-C8-haloalkylcarbonylamino having from 1 to 5 halogen atoms, C1-C8-alkylthio, C1-C8-haloalkylthio having from 1 to 5 halogen atoms, C1-C8-alkylsulfinyl, C1-C8-haloalkylsulfinyl having from 1 to 5 halogen atoms, C1-C8-alkylsulfonyl, C1-C8-haloalkylsulfonyl having from 1 to 5 halogen atoms, C1-C8-alkylsulfonylamino, C1-C8-haloalkylsulfonylamino having from 1 to 5 halogen atoms, sulfamoyl, C1-C8-alkylsulfamoyl and di-C1-C8-alkylsulfamoyl.

[0062] It is also preferred that R 4 and R 5Independently selected from hydrogen; halogen cyano; hydroxy; C1-C6-alkyl; C1-C6-hydroxyalkyl; C1-C6-alkoxy; C1-C6-haloalkyl; -O-C(=O)-C1-C6-alkyl; C3-C6-carbocycle; 4-, 5- or 6-membered non-aromatic heterocyclic group; -C(=O)-NH2; -C(=O)-NH(C1-C6-alkyl); -C(=O)-N(C1-C6-alkyl)2; -C(=O)-OH; -C(=O)-O-C1-C6-alkyl; aryl; 5- to 9-membered heteroaryl; -C1-C6-alkyl-C1-C6-alkoxy; -C1-C6-alkyl-C1-C6-haloalkyl; -C1-C6-alkyl-C3-C6-carbocycle; -C1-C6-alkyl-4-, 5- or 6-membered non-aromatic heterocyclic group; -C1-C6-alkyl-aryl; -C1-C6-alkyl-hydroxyaryl; -C1-C6-alkyl-5- to 9-membered heteroaryl; -C1-C6-alkyl-S-C1-C6-alkyl; -C1-C6-alkyl-S-C(=O)-C1-C6-alkyl; -C1-C6-alkyl-O-(C=O)-C1-C6-alkyl; -C1-C6-alkyl-C(=O)-NH2; -C1-C6-alkyl-C(=O)-NH(C1-C6-alkyl); -C1-C6-alkyl-C(=O)-N(C1-C6-alkyl)2; -C1-C6-alkyl-C(=O)-OH; -C1-C6-alkyl-C(=O)-O-C1-C6-alkyl; -C1-C6-alkyl-NH-C(=NH)-NH2; -S-C1-C6-alkyl; -S-C(=O)-C1-C6-alkyl; -S-C(=O)-O-C1-C6-alkyl; -S-C(=S)-O-C1-C6-alkyl; -S-C(=O)-S-C1-C6-alkyl; -S-C(=O)-NH2; -S-C(=O)-NH(C1-C6-alkyl); -S-C(=O)-NH(C1-C6-alkyl)2; -S-C(=S)-NH2; -S-C(=S)-NH(C1-C6-alkyl); -S-C(=S)-NH(C1-C6-alkyl)2; -C1-C6-alkyl-S-C(=O)-O-C1-C6-alkyl; -C1-C6-alkyl-S-C(=O)-S-C1-C6-alkyl; -C1-C6-alkyl-S-C(=O)-NH2; -C1-C6-alkyl-S-C(=O)-NH(C1-C6-alkyl); -C1-C6-alkyl-S-C(=O)-NH(C1-C6-alkyl)2; -C1-C6-alkyl-S-C(=S)-NH2; -C1-C6-alkyl-S-C(=S)-NH(C1-C6-alkyl); -C1-C6-alkyl-S-C(=S)-NH(C1-C6-alkyl)2, wherein acyclic R 4 、R5 The group may be substituted by one or more R w substituents, where the cyclic R 4 -, R 5 group may be substituted by one or more R x substituents, where R 4 and R 5 at least one of which is hydrogen, C1-C6-alkyl or C3-C6-cycloalkyl, or R 4 and R 5 together with the carbon atom to which they are attached form a 3- to 6-membered heterocycle, where the 3- to 6-membered heterocycle may be substituted by one or more R x substituents, where R w are independently selected from nitro, hydroxy, cyano, carboxy, amino, thioalkyl, pentafluoro-λ 6 -thioalkyl, formyl, carbamoyl, carbamate, C3-C7-cycloalkyl, C3-C7-halocycloalkyl having 1 to 5 halogen atoms, C1-C8-alkylamino, di-C1-C8-alkylamino, C1-C8-alkoxy, C1-C8-haloalkoxy having 1 to 5 halogen atoms, C1-C8-alkylthio, C1-C8-haloalkylthio having 1 to 5 halogen atoms, C1-C8-alkylcarbonyl, C1-C8-haloalkylcarbonyl having 1 to 5 halogen atoms, C1-C8-alkylcarbamoyl, di-C1-C8-alkylcarbamoyl, C1-C8-alkoxycarbonyl, C1-C8-haloalkoxycarbonyl having 1 to 5 halogen atoms, C1-C8-alkylcarbonyloxy, C1-C8-haloalkylcarbonyloxy having 1 to 5 halogen atoms, C1-C8-alkylcarbonylamino, C1-C8-haloalkylcarbonylamino having 1 to 5 halogen atoms, C1-C8-alkylsulfinyl, C1-C8-haloalkylsulfinyl having 1 to 5 halogen atoms, C1-C8-alkylsulfonyl, C1-C8-haloalkylsulfonyl having 1 to 5 halogen atoms, C1-C8-alkylsulfonylamino, C1-C8-haloalkylsulfonylamino having 1 to 5 halogen atoms, sulfamoyl, C1-C8-alkylsulfamoyl and di-C1-C8-alkylsulfamoyl, where R x are independently selected from halogen nitro, hydroxy, cyano, carboxy, amino, thioalkyl, pentafluoro-λ 6-thioalkyl, formyl, carbamoyl, carbamate, C1-C8-alkyl, C3-C7-cycloalkyl, C1-C8-haloalkyl having from 1 to 5 halogen atoms, C3-C7-halocycloalkyl having from 1 to 5 halogen atoms, C2-C8-alkenyl, C2-C8-alkynyl, C1-C8-alkylamino, di-C1-C8-alkylamino, C1-C8-alkoxy, C1-C8-haloalkoxy having from 1 to 5 halogen atoms, C1-C8-alkylthio, C1-C8-haloalkylthio having from 1 to 5 halogen atoms, C1-C8-alkylcarbonyl, C1-C8-haloalkylcarbonyl having from 1 to 5 halogen atoms, C1-C8-alkylcarbamoyl, di-C1-C8-alkylcarbamoyl, C1-C8-alkoxycarbonyl, C1-C8-haloalkoxycarbonyl having from 1 to 5 halogen atoms, C1-C8-alkylcarbonyloxy, C1-C8-haloalkylcarbonyloxy having from 1 to 5 halogen atoms, C1-C8-alkylcarbonylamino, C1-C8-haloalkylcarbonylamino having from 1 to 5 halogen atoms, C1-C8-alkylthio, C1-C8-haloalkylthio having from 1 to 5 halogen atoms, C1-C8-alkylsulfinyl, C1-C8-haloalkylsulfinyl having from 1 to 5 halogen atoms, C1-C8-alkylsulfonyl, C1-C8-haloalkylsulfonyl having from 1 to 5 halogen atoms, C1-C8-alkylsulfonylamino, C1-C8-haloalkylsulfonylamino having from 1 to 5 halogen atoms, sulfamoyl, C1-C8-alkylsulfamoyl and di-C1-C8-alkylsulfamoyl.

[0063] Also preferably excluded are compounds in which R 4 and R 5 together with the carbon atom to which they are attached form cyclopropyl.

[0064] Also preferably, if R 4 and R 5 are each independently selected from hydrogen, C1-C6-alkyl, C1-C6-hydroxyalkyl, C3-C6-carbocycle, aryl, -C1-C6-alkyl-C1-C6-alkoxy, -C1-C6-alkyl-C3-C6-carbocycle, C1-C6-alkyl-O-(C=O)-C1-C6-alkyl, -C1-C6-alkyl-C(=O)-OH, -C1-C6-alkyl-aryl, -C1-C6-alkyl-S-C1-C6-alkyl, where at least one of R 4 and R 5 is hydrogen, C1-C6-alkyl or C3-C6-carbocycle, n is 0 and W is oxygen, Y is NR 8 wherein R 8 is selected from hydrogen, C1-C6-alkyl, then Z is selected from cyano, -C(=O)-SR a, -C(=S)-NR b R c or -C(=O)-NH-CR d R e -C(=O)-OR a 。

[0065] According to another embodiment, R 1 and R 2 are independently preferably selected from F, Cl, Br, I, cyano, CH3 and preferably independently from each other are selected from F, Cl, Br, I.

[0066] According to another embodiment, R 1 is preferably selected from CN, Br, Cl, F, CHF2, CF3, preferably selected from CN, Br, Cl, F.

[0067] According to another embodiment, R 2 is preferably selected from Br, Cl, F, CHF2, CF3.

[0068] In yet another preferred embodiment, R 3 is selected from hydrogen, F, Cl, Br, I, cyano, CH3, CHF2, CF3, preferably selected from hydrogen, F, Cl, Br, I, cyano, CH3.

[0069] In another preferred embodiment, R 3 is selected from Br, Cl, F, CN, Me, CHF2, CF3.

[0070] Also preferably, the compound of formula (I) having the following combination of R 1 , R 2 and R 3

[0071] <![CDATA[R 1 > <![CDATA[R 2 > <![CDATA[R 3 > Halogen Halogen Halogen Halogen Halogen CN CN Halogen Halogen Halogen CN Halogen Halogen Halogen <![CDATA[Me, CF3 or CHF2]]>

[0072] Also preferably, R 3 is not hydrogen.

[0073] Also preferably, the compound of formula (I) wherein R 3 is not hydrogen and does not include the following compounds wherein R 1 , R 2 and R 3 are independently selected from halogen and C1-C6 alkyl; W is oxygen; Y is NH; R 4 and R 5 together with the carbon atom to which they are attached form cyclopropyl; n is 0; Z is selected from -C(=O)-OR a , -C(=O)-NR b R c 。

[0074] It is also preferred that R 1 , R 2 and R 3 at least one of which is a cyano group.

[0075] In another preferred embodiment, R 4 is selected from: hydrogen, C1-C6-alkyl, C1-C6-hydroxyalkyl, C3-C6-carbocycle, C(=O)-OH, -C(=O)-O-C1-C6-alkyl, -C1-C6-alkyl-C1-C6-alkoxy, -C1-C6-alkyl-C1-C6-haloalkyl, -C1-C6-alkyl-C3-C6-carbocycle, -C1-C6-alkyl-aryl, -C1-C6-alkyl-hydroxyaryl, -C1-C6-alkyl-S-C1-C6-alkyl-, -C1-C6-alkyl-C(=O)-NH2, -C1-C6-alkyl-C(=O)-OH, -C1-C6-alkyl-C(=O)-O-C1-C6-alkyl, R5 is selected from hydrogen, C1-C6-alkyl or C3-C6-carbocycle; or R 4 and R 5 together with the carbon atom to which they are attached form a C3-C6-carbocycle.

[0076] It is also preferred that R 6 and R 7 are independently selected from hydrogen, C1-C3-alkyl, C3-C6-carbocycle.

[0077] In another preferred embodiment, n is 0.

[0078] It is also preferred that the compound of formula (I) wherein n is 0 and does not include the case where R 1 , R 2 and R 3 are independently selected from halogen and C1-C6-alkyl; W is oxygen; Y is NH; R 4 and R 5 together with the carbon atom to which they are attached form a cyclopropyl; n is 0; Z is selected from -C(=O)-OR a , -C(=O)-NR b R c .

[0079] Also preferred is that if W is oxygen.

[0080] It is also preferred that the compound of formula (I) wherein W is oxygen and does not include the following compounds, wherein R 1 , R 2 and R 3 are independently selected from halogen and C1-C6-alkyl; W is oxygen; Y is NH; R 4 and R 5Together with the carbon atoms to which they are attached, form a cyclopropyl; n is 0; Z is selected from -C(=O)-OR a 、-C(=O)-NR b R c 。

[0081] It is also preferred that, if Y is selected from NH, N-OCH 3 、N-OH, most preferably NH.

[0082] Compounds of formula (I) are also preferred, wherein Y is NH and which do not include the following compounds, wherein R 1 、R 2 and R 3 are independently selected from halogen and C1-C6-alkyl; W is oxygen; Y is NH; R 4 and R 5 Together with the carbon atoms to which they are attached, form a cyclopropyl; n is 0; Z is selected from -C(=O)-OR a 、-C(=O)-NR b R c 。

[0083] According to another embodiment, Z is selected from cyano, -C(=O)-OR a 、-C(=O)-SR a 、-C(=O)-NR b R c 、-C(=S)-NR b R c or -C(=O)-NH-CR d R e -C(=O)-OR a and is preferably -C(=O)-OR a 。

[0084] According to another embodiment, Z is selected from cyano, -C(=O)-OR a 、-C(=O)-SR a 、-C(=O)-NR b R c 、-C(=S)-NR b R c 。

[0085] In another preferred embodiment

[0086] R 1 and R 2 are independently of each other selected from F, Cl, Br, I, cyano, CH3 and are preferably independently of each other selected from F, Cl, Br, I;

[0087] R 3Selected from hydrogen, F, Cl, Br, I, cyano, CH3, CHF2, CF3 and preferably selected from hydrogen, F, Cl, Br, I, cyano, CH3;

[0088] R 4 Selected from hydrogen, C1-C6-alkyl, C1-C6-hydroxyalkyl, C3-C6-carbocycle, C(=O)-OH,

[0089] -C(=O)-O-C1-C6-alkyl, -C1-C6-alkyl-C1-C6-alkoxy, -C1-C6-alkyl

[0090] -C1-C6-haloalkyl, -C1-C6-alkyl-C3-C6-carbocycle, -C1-C6-alkyl-aryl,

[0091] -C1-C6-alkyl-hydroxyaryl, -C1-C6-alkyl-S-C1-C6-alkyl-, -C1-C6-alkyl

[0092] -C(=O)-NH2, -C1-C6-alkyl-C(=O)-OH, -C1-C6-alkyl-C(=O)-O-C1-C6-alkyl, R 5 Selected from hydrogen, C1-C6-alkyl or C3-C6-carbocycle, or R 4 and R 5 together with the carbon atom to which they are attached form a C3-C6-carbocycle;

[0093] R 6 and R 7 independently selected from hydrogen, C1-C6-alkyl, C3-C6-carbocycle, or R 6 and R 7 together with the carbon atom to which they are attached form a C3-C6-carbocycle or a 3- to 6-membered heterocycle;

[0094] n is 0;

[0095] W is oxygen;

[0096] Y is selected from NH, N-OCH3, N-OH, preferably NH;

[0097] Z is selected from cyano, -C(=O)-OR a 、-C(=O)-SR a 、-C(=O)-NR b R c 、

[0098] -C(=S)-NR b R c or -C(=O)-NH-CR d R e -C(=O)-ORa , preferably

[0099] -C(=O)-OR a .

[0100] In another preferred embodiment

[0101] R 1 and R 2 are independently selected from F, Cl, Br, I;

[0102] R 3 is selected from hydrogen, F, Cl, Br, I, cyano, CH3;

[0103] R 4 is selected from hydrogen, C1-C6-alkyl, C1-C6-hydroxyalkyl, C3-C6-carbocycle, C(=O)-OH,

[0104] -C(=O)-O-C1-C6-alkyl, -C1-C6-alkyl-C1-C6-alkoxy, -C1-C6-alkyl

[0105] -C1-C6-haloalkyl, -C1-C6-alkyl-C3-C6-carbocycle, -C1-C6-alkyl-aryl,

[0106] -C1-C6-alkyl-hydroxyaryl, -C1-C6-alkyl-S-C1-C6-alkyl-, -C1-C6-alkyl

[0107] -C(=O)-NH2, -C1-C6-alkyl-C(=O)-OH, -C1-C6-alkyl-C(=O)-O-C1-C6-alkyl, R 5 is selected from hydrogen, C1-C6-alkyl or C3-C6-carbocycle, or R 4 and R 5 together with the carbon atom to which they are attached form a C3-C6-carbocycle;

[0108] R 6 and R 7 are independently selected from hydrogen, C1-C6-alkyl, C3-C6-carbocycle, or R 6 and R 7 together with the carbon atom to which they are attached form a C3-C6-carbocycle or a 3- to 6-membered heterocycle;

[0109] n is 0;

[0110] W is oxygen;

[0111] Y is NH;

[0112] Z is -C(=O)-OR a .

[0113] In yet another embodiment, a compound of formula (I) is preferred, wherein R 1 , R 2 and R 3 are a combination selected from the following

[0114] <![CDATA[R 1 > <![CDATA[R 2 > <![CDATA[R 3 > Halogen Halogen Halogen Halogen Halogen CN CN Halogen Halogen Halogen CN Halogen Halogen Halogen <![CDATA[Me, CF3 or CHF2]]>

[0115] R 4 is selected from hydrogen, C1-C6-alkyl, C1-C6-hydroxyalkyl, C3-C6-carbocycle, C(=O)-OH, -C(=O)-O-C1-C6-alkyl, -C1-C6-alkyl-C1-C6-alkoxy, -C1-C6-alkyl-C1-C6-haloalkyl, -C1-C6-alkyl-C3-C6-carbocycle, -C1-C6-alkyl-aryl, -C1-C6-alkyl-hydroxyaryl, -C1-C6-alkyl-S-C1-C6-alkyl-, -C1-C6-alkyl-C(=O)-NH2, -C1-C6-alkyl-C(=O)-OH, -C1-C6-alkyl-C(=O)-O-C1-C6-alkyl, R 5 is selected from hydrogen, C1-C6-alkyl or C3-C6-carbocycle, or R 4 and R 5 together with the carbon atom to which they are attached form a C3-C6-carbocycle;

[0116] R 6 and R 7 are independently selected from hydrogen, C1-C6-alkyl, C3-C6-carbocycle, or R 6 and R 7 together with the carbon atom to which they are attached form a C3-C6-carbocycle or a 3- to 6-membered heterocycle;

[0117] n is 0;

[0118] W is oxygen;

[0119] Y is selected from NH, N-OCH3, N-OH, and is preferably NH;

[0120] Z is selected from cyano, -C(=O)-OR a , -C(=O)-SR a , -C(=O)-NR b R c , -C(=S)-NR b R c

[0121] or -C(=O)-NH-CR d R e -C(=O)-OR a , and is preferably -C(=O)-OR a。

[0122] In another embodiment, if R 1 = halogen, then R 2 = cyano, C1-C6-alkyl or C1-C6-haloalkyl and R 3 = cyano, C1-C6-alkyl or C1-C6-haloalkyl. In another embodiment, if R 1 = halogen, then R 2 = cyano, C1-C6-alkyl or C1-C6-haloalkyl and R 3 = hydrogen or halogen. In another embodiment, if R 2 = halogen, then R 1 = cyano, C1-C6-alkyl or C1-C6-haloalkyl and R 3 = cyano, C1-C6-alkyl or C1-C6-haloalkyl. In another embodiment, if R 2 = halogen, then R 1 = cyano, C1-C6-alkyl or C1-C6-haloalkyl and R 3 = hydrogen or halogen. In another embodiment, if R 1 and R 2 = halogen, then R 2 is different from R 1 , and R 3 = hydrogen or halogen. In another embodiment, if R 1 and R 2 = halogen, then R 2 is different from R 1 and R 3 = cyano, C1-C6-alkyl or C1-C6-haloalkyl. In another embodiment, if R 1 and R 2 = halogen, then R 3 = cyano, C1-C6-alkyl or C1-C6-haloalkyl. In another embodiment, if R 1 and R 2 = halogen, then R 3 = hydrogen or halogen. In another embodiment, if R 1 and R 2 = halogen, then R 3 = hydrogen. In another embodiment, if R 1 and R 2 = halogen, then R 3 = halogen.

[0123] In another embodiment, R 1is a halogen, a cyano group, a C1-C6-alkyl group or a C1-C6-haloalkyl group. In another embodiment, R 1 is a halogen, a cyano group, a C1-C3-alkyl group or a C1-C3-haloalkyl group. In another embodiment, R 1 is a halogen, a cyano group or a C1-C3-alkyl group. In another embodiment, R 1 is a C1-C3-haloalkyl group. In another embodiment, R 1 is a halogen, a cyano group, a methyl group, a trifluoromethyl group or a difluoromethyl group. In another embodiment, R 1 is a halogen, a cyano group or a methyl group. In another embodiment, R 1 is a trifluoromethyl group or a difluoromethyl group.

[0124] In another embodiment, R 2 is a halogen, a cyano group, a C1-C6-alkyl group or a C1-C6-haloalkyl group. In another embodiment, R 2 is a halogen, a cyano group, a C1-C3-alkyl group or a C1-C3-haloalkyl group. In another embodiment, R 2 is a halogen, a cyano group or a C1-C3-alkyl group. In another embodiment, R 2 is a C1-C3-haloalkyl group. In another embodiment, R 2 is a halogen, a cyano group, a methyl group, a trifluoromethyl group or a difluoromethyl group. In another embodiment, R 2 is a halogen, a cyano group or a methyl group. In another embodiment, R 2 is a trifluoromethyl group or a difluoromethyl group.

[0125] In another embodiment, R 3 is hydrogen, a halogen, a cyano group, a C1-C6-alkyl group or a C1-C6-haloalkyl group. In another embodiment, R 3 is hydrogen, a halogen, a cyano group, a C1-C3-alkyl group or a C1-C3-haloalkyl group. In another embodiment, R 3 is hydrogen, a halogen, a cyano group, a methyl group, a trifluoromethyl group or a difluoromethyl group.

[0126] In another embodiment, R 4 and R 5Each independently selected from halogen; cyano; hydroxy; C1-C6-alkoxy; C1-C6-haloalkyl; -O-C(=O)-C1-C6-alkyl; 4-, 5- or 6-membered non-aromatic heterocyclic group; -C(=O)-NH2; -C(=O)-NH(C1-C6-alkyl); -C(=O)-N(C1-C6-alkyl)2; -C(=O)-OH; -C(=O)-O-C1-C6-alkyl; 5- to 9-membered heteroaryl; -C1-C6-alkyl-C1-C6-haloalkyl; -C1-C6-alkyl-4-, 5- or 6-membered non-aromatic heterocyclic group; -C1-C6-alkyl-hydroxyaryl; -C1-C6-alkyl-5- to 9-membered heteroaryl; -C1-C6-alkyl-S-C(=O)-C1-C6-alkyl; -C1-C6-alkyl-C(=O)-NH2; -C1-C6-alkyl-C(=O)-NH(C1-C6-alkyl); -C1-C6-alkyl-C(=O)-N(C1-C6-alkyl)2; -C1-C6-alkyl-C(=O)-O-C1-C6-alkyl; -C1-C6-alkyl-NH-C(=NH)-NH2; -S-C1-C6-alkyl; -S-C(=O)-C1-C6-alkyl; -S-C(=O)-O-C1-C6-alkyl; -S-C(=S)-O-C1-C6-alkyl; -S-C(=O)-S-C1-C6-alkyl; -S-C(=O)-NH2; -S-C(=O)-NH(C1-C6-alkyl); -S-C(=O)-NH(C1-C6-alkyl)2; -S-C(=S)-NH2; -S-C(=S)-NH(C1-C6-alkyl); -S-C(=S)-NH(C1-C6-alkyl)2; -C1-C6-alkyl-S-C(=O)-O-C1-C6-alkyl; -C1-C6-alkyl-S-C(=O)-S-C1-C6-alkyl; -C1-C6-alkyl-S-C(=O)-NH2; -C1-C6-alkyl-S-C(=O)-NH(C1-C6-alkyl); -C1-C6-alkyl-S-C(=O)-NH(C1-C6-alkyl)2; -C1-C6-alkyl-S-C(=S)-NH2; -C1-C6-alkyl-S-C(=S)-NH(C1-C6-alkyl); -C1-C6-alkyl-S-C(=S)-NH(C1-C6-alkyl)2, wherein acyclic R 4 、R 5 groups may be substituted by one to more R w substituents, wherein cyclic R 4 、R 5 groups may be substituted by one to more R x substituents, wherein R 4 and R 5At least one of them is hydrogen, C1-C6-alkyl or C3-C6-carbocycle. In another embodiment, R 4 and R 5 are independently selected from hydrogen, C1-C6-alkyl, C1-C6-hydroxyalkyl, C3-C6-carbocycle, aryl, -C1-C6-alkyl-C1-C6-alkoxy, -C1-C6-alkyl-C3-C6-carbocycle, C1-C6-alkyl-O-(C=O)-C1-C6-alkyl, -C1-C6-alkyl-C(=O)-OH; -C1-C6-alkyl-aryl, -C1-C6-alkyl-S-C1-C6-alkyl, wherein the acyclic R 4 and R 5 groups may be substituted by one or more R w substituents, wherein the cyclic R 4 and R 5 groups may be substituted by one or more R x substituents, wherein at least one of R 4 and R 5 is hydrogen, C1-C6-alkyl or C3-C6-carbocycle; or R 4 and R 5 together with the carbon atom to which they are attached form a C3-C6-carbocycle or a 3- to 6-membered heterocycle, wherein the C3-C6-carbocycle and the 3- to 6-membered heterocycle may be substituted by one or more R x substituents. In another embodiment, R 4 is hydrogen, C1-C6-alkyl, C1-C6-hydroxyalkyl, C3-C6-carbocycle, C(=O)-OH, -C(=O)-O-C1-C6-alkyl, -C1-C6-alkyl-C1-C6-alkoxy, -C1-C6-alkyl-C1-C6-haloalkyl, -C1-C6-alkyl-C3-C6-carbocycle, -C1-C6-alkyl-aryl, -C1-C6-alkyl-hydroxyaryl, -C1-C6-alkyl-S-C1-C6-alkyl-, -C1-C6-alkyl-C(=O)-NH2, -C1-C6-alkyl-C(=O)-OH, -C1-C6-alkyl-C(=O)-O-C1-C6-alkyl, R5 is hydrogen, C1-C6-alkyl or C3-C6-carbocycle, or R 4 and R 5 together with the carbon atom to which they are attached form a C3-C6-carbocycle. In another embodiment, R 4is hydrogen, C1-C6-alkyl, C3-C6-cycloalkyl, -C1-C6-alkyl-C1-C6-haloalkyl, -C1-C6-alkyl-C3-C6-cycloalkyl, -C1-C6-alkyl-aryl, -C1-C6-alkyl-hydroxyaryl, -C1-C6-alkyl-S-C1-C6-alkyl-, R5 is hydrogen or C1-C6-alkyl, or R 4 and R 5 together with the carbon atom to which they are attached form a C3-C6-cycloalkyl. In another embodiment, R 4 is hydrogen, C1-C6-alkyl, C3-C6-cycloalkyl, -C1-C6-alkyl-C1-C6-haloalkyl, -C1-C6-alkyl-C3-C6-cycloalkyl, -C1-C6-alkyl-aryl, -C1-C6-alkyl-hydroxyaryl, -C1-C6-alkyl-S-C1-C6-alkyl-, R5 is hydrogen or C1-C6-alkyl. In another embodiment, R 4 and R 5 together with the carbon atom to which they are attached form a C3-C6-cycloalkyl or a 3- to 6-membered heterocycle. In another embodiment, R 4 and R 5 together with the carbon atom to which they are attached form a C3-C6-cycloalkyl. In another embodiment, R 4 and R 5 together with the carbon atom to which they are attached form cyclopropyl or cyclobutyl.

[0127] In another embodiment, n is 0. In another embodiment, n is 1.

[0128] In another embodiment, W is oxygen. In another embodiment, W is sulfur.

[0129] In another embodiment, n is 0 and W is oxygen.

[0130] Compounds of formula (I) are also preferred, wherein n is 0 and W is oxygen, and which do not include compounds where R 1 , R 2 and R 3 are independently selected from halogen and C1-C6-alkyl; W is oxygen; Y is NH; R 4 and R 5 together with the carbon atom to which they are attached form cyclopropyl; n is 0; Z is selected from -C(=O)-OR a , -C(=O)-NR b R c .

[0131] In another embodiment n is 0, W is oxygen and R 8 is H.

[0132] Also preferred are compounds of formula (I) wherein n is 0, W is oxygen and R 8 is H, and which do not include the compounds where R 1 , R 2 and R 3 are independently selected from halogen and C1-C6-alkyl; W is oxygen; Y is NH; R 4 and R 5 together with the carbon atom to which they are attached form cyclopropyl; n is 0; Z is selected from -C(=O)-OR a , -C(=O)-NR b R c .

[0133] In another embodiment n is 0, W is oxygen, R 8 is H and R 3 is not H.

[0134] Also preferred are compounds of formula (I) wherein n is 0, W is oxygen, R 8 is H and R 3 is not H, and which do not include the compounds where R 1 , R 2 and R 3 are independently selected from halogen and C1-C6-alkyl; W is oxygen; Y is NH; R 4 and R 5 together with the carbon atom to which they are attached form cyclopropyl; n is 0; Z is selected from -C(=O)-OR a , -C(=O)-NR b R c .

[0135] In another embodiment n is 0, W is oxygen, R 8 is H and R 3 is selected from Br, Cl, F, CN, Me, CHF2, CF3.

[0136] Also preferred are compounds of formula (I) wherein n is 0, W is oxygen, R 8 is H and R 3 is selected from Br, Cl, F, CN, Me, CHF2, CF3, and which do not include the compounds where R 1 , R 2 and R 3 are independently selected from halogen and C1-C6-alkyl; W is oxygen; Y is NH; R 4 and R 5 together with the carbon atom to which they are attached form cyclopropyl; n is 0; and Z is selected from -C(=O)-OR a , -C(=O)-NR b R c .

[0137] In another embodiment, n is 0, W is oxygen, R 8 is H and R 1 is selected from CN, Br, Cl, F, CHF2, CF3.

[0138] Also preferred are the compounds of formula (I) wherein n is 0, W is oxygen, R 8 is H and R 1 is selected from CN, Br, Cl, F, CHF2, CF3, and which do not include the compounds where R 1 , R 2 and R 3 are independently selected from halogen and C1-C6-alkyl; W is oxygen; Y is NH; R 4 and R 5 together with the carbon atom to which they are attached form cyclopropyl; n is 0; and Z is selected from -C(=O)-OR a , -C(=O)-NR b R c .

[0139] In another embodiment, n is 0, W is oxygen, R 8 is H and R 1 is selected from CN, Br, Cl, F.

[0140] Also preferred are the compounds of formula (I) wherein n is 0, W is oxygen, R 8 is H and R 1 is selected from CN, Br, Cl, F, and which do not include the compounds where R 1 , R 2 and R 3 are independently selected from halogen and C1-C6-alkyl; W is oxygen; Y is NH; R 4 and R 5 together with the carbon atom to which they are attached form cyclopropyl; n is 0; and Z is selected from -C(=O)-OR a , -C(=O)-NR b R c .

[0141] In another embodiment, n is 0, W is oxygen, R 8 is H and R 2 is selected from Br, Cl, F, CHF2, CF3.

[0142] Also preferred are the compounds of formula (I) wherein n is 0, W is oxygen, R 8 is H and R 2 is selected from Br, Cl, F, CHF2, CF3, and which do not include the compounds where R 1 , R 2 and R3 Compounds when independently selected from halogen and C1-C6-alkyl; W is oxygen; Y is NH; R 4 and R 5 together with the carbon atom to which they are attached form cyclopropyl; n is 0; and Z is selected from -C(=O)-OR a 、-C(=O)-NR b R c .

[0143] In another embodiment, n is 0, W is oxygen, R 8 is H and R 1 、R 2 and R 3 at least one of which is cyano.

[0144] In another embodiment, n is 0, W is oxygen, R 8 is H, R 3 is selected from Br, Cl, F, CN, Me, CHF2, CF3, and R 1 is selected from CN, Br, Cl, F, CHF2, CF3, Me.

[0145] Also preferred are compounds of formula (I) wherein n is 0, W is oxygen, R 8 is H and R 3 is selected from Br, Cl, F, CN, Me, CHF2, CF3, and R 1 is selected from CN, Br, Cl, F, CHF2, CF3, Me, and wherein excluded are the compounds when R 1 、R 2 and R 3 are independently selected from halogen and C1-C6-alkyl; W is oxygen; Y is NH; R 4 and R 5 together with the carbon atom to which they are attached form cyclopropyl; n is 0; and Z is selected from -C(=O)-OR a 、-C(=O)-NR b R c .

[0146] In another embodiment, n is 0, W is oxygen, R 8 is H, R 3 is selected from Br, Cl, F, CN, Me, CHF2, CF3, and R 2 is selected from Br, Cl, F, CHF2, CF3, Me.

[0147] Also preferred are compounds of formula (I) wherein n is 0, W is oxygen, R 8 is H and R 3 is selected from Br, Cl, F, CN, Me, CHF2, CF3, and R2 Selected from Br, Cl, F, CHF2, CF3, Me, and excluding the compound when R 1 , R 2 and R 3 are independently selected from halogen and C1-C6-alkyl; W is oxygen; Y is NH; R 4 and R 5 together with the carbon atom to which they are attached form cyclopropyl; n is 0; and Z is selected from -C(=O)-OR a , -C(=O)-NR b R c .

[0148] In another embodiment, n is 0, W is oxygen, R 8 is H, R 3 is selected from Br, Cl, F, CN, Me, CHF2, CF3, R 2 is selected from Br, Cl, F, CHF2, CF3 and R 1 is selected from CN, Br, Cl, F, CHF2, CF3, Me.

[0149] Also preferred are compounds of formula (I) wherein n is 0, W is oxygen, R 8 is H and R 3 is selected from Br, Cl, F, CN, Me, CHF2, CF3, R 2 is selected from Br, Cl, F, CHF2, CF3 and R 1 is selected from CN, Br, Cl, F, CHF2, CF3, Me, and excluding the compound when R 1 , R 2 and R 3 are independently selected from halogen and C1-C6-alkyl; W is oxygen; Y is NH; R 4 and R 5 together with the carbon atom to which they are attached form cyclopropyl; n is 0; and Z is selected from -C(=O)-OR a , -C(=O)-NR b R c .

[0150] In another embodiment, Y is NR 8 , wherein R 8 is hydrogen. In another embodiment, Y is NR 8 , wherein R 8 is C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-cyanoalkyl, hydroxy, C1-C6-alkoxy or C3-C6-carbocycle.

[0151] In another embodiment, Z is selected from cyano, -C(=O)-SRa 、 -C(=O)-NR b R c 、 -C(=S)-NR b R c or -C(=O)-NH-CR d R e -C(=O)-OR a 。In another embodiment, Z is -C(=O)-OR a 。

[0152] In another embodiment, if R 1 is C1-C6-haloalkyl or R 2 is C1-C6-haloalkyl and R 4 is selected from hydrogen, C1-C6-alkyl and R 5 is selected from hydrogen, C1-C6-alkyl, and n is 0, W is oxygen, then Z is selected from cyano, -C(=O)-SR a 、 -C(=O)-NR b R c 、 -C(=S)-NR b R c or -C(=O)-NH-CR d R e -C(=O)-OR a 。

[0153] In another embodiment, if R 4 and R 5 are independently selected from hydrogen, C1-C6-alkyl, C1-C6-hydroxyalkyl, C3-C6-carbocycle, aryl, -C1-C6-alkyl-C1-C6-alkoxy, -C1-C6-alkyl-C3-C6-carbocycle, C1-C6-alkyl-O-(C=O)-C1-C6-alkyl, -C1-C6-alkyl-C(=O)-OH; -C1-C6-alkyl-aryl, -C1-C6-alkyl-S-C1-C6-alkyl, where at least one of R 4 and R 5 is hydrogen, C1-C6-alkyl or C3-C6-carbocycle, and n is 0, W is oxygen, Y is NR 8 ,where R 8 is selected from hydrogen, C1-C6-alkyl, then Z is selected from cyano, -C(=O)-SR a 、 -C(=S)-NR b R c or -C(=O)-NH-CR d R e -C(=O)-OR a 。

[0154] In another embodiment, if R 1 、R 2 and R 3 are the following combinations

[0155] <![CDATA[R 1 > <![CDATA[R 2 > <![CDATA[R 3 > Cl Cl Halogen Br Br Halogen

[0156] then R 4 and R 5 together with the carbon atom to which they are attached form cyclopropyl, and n is 0, W is oxygen, Y is NH, then Z is selected from cyano, -C(=O)-SR a 、-C(=O)-NR b R c 、-C(=S)-NR b R c or -C(=O)-NH-CR d R e -C(=O)-OR a .

[0157] In another embodiment, if R 1 、R 2 and R 3 are the following combinations

[0158] <![CDATA[R 1 > <![CDATA[R 2 > <![CDATA[R 3 > Cl Cl Br Cl Cl I Br Br I

[0159] R 4 is selected from C1-C6-alkyl, -C1-C6-alkyl-aryl, -C1-C6-alkyl-hydroxyaryl, -C1-C6-alkyl-S-C1-C6-alkyl and R 5 is hydrogen, n is 0, W is oxygen, Y is NH, then Z is selected from cyano, -C(=O)-SR a 、-C(=O)-NR b R c 、-C(=S)-NR b R c or -C(=O)-NH-CR d R e -C(=O)-OR a .

[0160] Also preferred are compounds I.0001 to I.1070 disclosed in Tables I.1 and I.2 in the experimental section.

[0161] Another aspect of the present invention relates to a composition comprising at least one compound of formula (I) according to the present invention and at least one agriculturally suitable adjuvant.

[0162] Another aspect of the present invention relates to a method for controlling bacterial and / or fungal diseases, which method comprises the step of applying at least one compound of formula (I) according to the present invention or the composition according to the present invention to plants, plant parts, seeds, fruits or the soil in which the plants grow.

[0163] Another aspect of the present invention relates to the use of the compounds or the compositions according to the present invention in controlling bacterial and / or fungal diseases on plants or plant parts. They are preferably used for controlling fungal diseases of plants or plant parts.

[0164] Another aspect of the present invention relates to the use of the compounds or the compositions according to the present invention for controlling nematodes on plants or plant parts.

[0165] Another aspect of the present invention relates to the use of the compounds or the compositions according to the present invention for controlling viruses on plants or plant parts.

[0166] Preferably, the compounds or compositions of the present invention are used against: diseases caused by powdery mildew pathogens (e.g., Podosphaera (Podosphaera leucotricha), Sphaerotheca (such as Sphaerotheca fuliginea)); diseases caused by rust pathogens (such as Uromyces (such as Uromyces appendiculatus)); diseases caused by the following pathogens: Oomycetes, such as Peronospora (such as Peronospora parasitica), Phytophthora (such as Phytophthora infestans), Plasmopara (such as Plasmopara viticola), Pseudoperonospora (such as Pseudoperonospora humuli or Pseudoperonospora cubensis), Pythium (such as Pythium ultimum); leaf spot and leaf blight diseases caused by, for example, Alternaria (such as Alternaria solani), Cercospora (such as Cercospora beticola), Colletotrichum (such as Colletotrichum lindemuthanium), Venturia (such as Venturia inaequalis); diseases caused by bacterial pathogens, such as Xanthomonas (such as Xanthomonas campestris pv. Campestris), Pseudomonas (such as Pseudomonas syringae pv. Tomato), Erwinia (such as Erwinia amylovora), Liberibacter (such as Liberibacter Candidatus), Ralstonia (such as Ralstonia solanacearum).

[0167] According to another aspect of the present invention, the compounds or compositions of the present invention are used as plant defense activators. The plant defense inducer according to the present invention is a compound or composition that stimulates the plant's own defense system.

[0168] The present invention also relates to the use of the compounds of formula (II) in crop protection

[0169]

[0170] wherein

[0171] R 1 and R 2 are each independently selected from halogen, cyano, C1-C3-alkyl or C1-C3-haloalkyl, where R 1 or R 2 is at least one halogen;

[0172] R 3 is selected from hydrogen, halogen, cyano, C1-C3-alkyl or C1-C3-haloalkyl,

[0173] A is selected from halogen and C1-C6-alkyl;

[0174] provided that compounds of formula (II) having the following combination of R 1 , R 2 and R 3 are excluded

[0175] <![CDATA[R 1 > <![CDATA[R 2 > <![CDATA[R 3 > Cl Cl Halogen Br Br Halogen Br Me H Cl Cl Methyl Br Br Methyl Br Br H Cl Cl H <![CDATA[CF3]]> Cl H Cl <![CDATA[CF3]]> H

[0176] In one embodiment, R 1 is halogen, cyano, C1-C3-alkyl or C1-C3-haloalkyl. In one embodiment, R 1 is halogen, cyano or C1-C3-alkyl. In one embodiment, R 1 is C1-C3-haloalkyl. In one embodiment, R 1 is halogen, cyano, methyl, trifluoromethyl or difluoromethyl. In one embodiment, R 1 is halogen, cyano or methyl. In one embodiment, R 1 is trifluoromethyl or difluoromethyl.

[0177] In one embodiment, R 2 is halogen, cyano, C1-C3-alkyl or C1-C3-haloalkyl. In one embodiment, R 2 is halogen, cyano or C1-C3-alkyl. In one embodiment, R 2 is C1-C3-haloalkyl. In one embodiment, R 2 is halogen, cyano, methyl, trifluoromethyl or difluoromethyl. In one embodiment, R 2 is halogen, cyano or methyl. In one embodiment, R 2 is trifluoromethyl or difluoromethyl.

[0178] In one embodiment, R 3 is hydrogen, halogen, cyano, C1-C3-alkyl or C1-C3-haloalkyl. In one embodiment, R 3 is hydrogen, halogen, cyano, methyl, trifluoromethyl or difluoromethyl.

[0179] In one embodiment, A is hydrogen. In one embodiment, A is hydrogen or a C1-C6-alkyl. In one embodiment, A is hydrogen or a C1-C3-alkyl. In one embodiment, A is hydrogen, methyl, ethyl or propyl.

[0180] In a preferred embodiment, R 1 and R 2 are each independently selected from halogen, cyano or a C1-C3-alkyl, wherein at least one of R 1 or R 2 is halogen.

[0181] Also preferred are compounds II.001 to II.104 disclosed in Table II.1 of the experimental section.

[0182] Also preferred is that the compound of formula (II) is used for controlling phytopathogenic fungi and / or bacteria on plants or plant parts. Most preferably, the compound of formula (II) is used for controlling fungal diseases on plants or plant parts.

[0183] Also preferred is that the compound of formula (II) is used for controlling nematodes on plants or plant parts.

[0184] Also preferred is that the compound of (II) is used for controlling viruses on plants or plant parts.

[0185] Preferably, the compounds or compositions of the present invention are used against: diseases caused by powdery mildew pathogens (such as Podosphaera (Podosphaera leucotricha), Sphaerotheca (such as Sphaerotheca fuliginea)); diseases caused by rust pathogens (such as Uromyces (such as Uromyces appendiculatus)); diseases caused by the following pathogens: Oomycetes, such as Peronospora (such as Peronospora parasitica), Phytophthora (such as Phytophthora infestans), Plasmopara (such as Plasmopara viticola), Pseudoperonospora (such as Pseudoperonospora humuli or Pseudoperonospora cubensis), Pythium (such as Pythium ultimum); leaf spot and leaf blight diseases caused by, for example, Alternaria (such as Alternaria solani), Cercospora (such as Cercospora beticola), Colletotrichum (such as Colletotrichum lindemuthanium), Venturia (such as Venturia inaequalis); diseases caused by bacterial pathogens, such as Xanthomonas (such as Xanthomonas campestris pv. Campestris), Pseudomonas (such as Pseudomonas syringae pv. Tomato), Erwinia (such as Erwinia amylovora), Liberibacter (such as Liberibacter Candidatus), Ralstonia (such as Ralstonia solanacearum).

[0186] According to another aspect of the present invention, the compounds of formula (II) of the present invention are used as plant defense activators. The plant defense inducer according to the present invention is a compound or composition that stimulates the plant's own defense system.

[0187] The present invention also relates to compounds of formula (II-A):

[0188]

[0189] wherein

[0190] R1 selected from halogen, cyano, methyl or C1-C2-haloalkyl;

[0191] R 2 selected from halogen, cyano or C1-C2-haloalkyl;

[0192] R 3 selected from halogen, cyano, methyl or C1-C2-haloalkyl;

[0193] wherein at least two of R 1 , R 2 or R 3 are hydrogen;

[0194] provided that compounds of formula (II-A) having the following combination of R 1 , R 2 and R 3 are excluded

[0195] <![CDATA[R 1 > <![CDATA[R 2 > <![CDATA[R 3 > Cl Cl Halogen Br Br Halogen Cl Cl Methyl Br Br Methyl Cl I F Br I I I I F I I Methyl I I I Methyl I F Methyl Br Br Methyl I I Br Cyano Br I Cyano I F Br Methyl Cl Br F

[0196] WO 2020 / 079205 discloses 3-fluoro-5-iodothiophene-2-carboxylic acid and 5-bromo-4-chloro-3-fluorothiophene-2-carboxylic acid; FR 3 052 451 discloses 5-chloro-3-fluoro-4-methylthiophene-2-carboxylic acid and 4,5-dichloro-3-fluorothiophene-2-carboxylic acid; HULLJOHN W JR et al.: "Development of potential manufacturing routes for substituted thiophenes - Preparation of halogenated 2-thiophenecarboxylic acid derivatives as building blocks for a new family of 2,6-dihaloaryl 1,2,4-triazole insecticides", BEILSTEIN JOURNAL OF ORGANIC CHEMISTRY, BIOMED CENTRAL, LONDON, UK, Vol. 3, No. 1, September 4, 2007 (2007-09-04), p. 23, XP021041099, ISSN: 1860-5397 discloses 3,5-dibromo-4-methylthiophene-2-carboxylic acid; KOCHANNY et al.: "Substituted thiophene-anthranilamides as potent inhibitors of human factor Xa", BIOORGANIC & MEDICINAL CHEMISTRY: A TETRAHEDRON PUBLICATION FOR THE RAPID DISSEMINATION OF FULL ORIGINAL RESEARCH PAPERS AND CRITICAL REVIEWS ON BIOMOLECULAR CHEMISTRY, MEDICINAL CHEMISTRY AND RELATED DISCIPLINES, ELSEVIER, NL, Vol. 15, No. 5, January 31, 2007 (2007-01-31), pp. 2127-2146, XP005867178, ISSN: 0968-0896, DOI: 10.1016 / J.BMC.2006.12.019 discloses 3-chloro-5-(chloromethyl)-4-methylthiophene-2-carboxylic acid and STEINKOPF W et al.: "Thiophene series. XXXVII."Iodine derivatives of 3 - thiotolene", JUSTUS LIEBIGS ANNALEN DER CHEMIE, VERLAG CHEMIE GMBH, Germany, Volume 532, January 1, 1937 (1937 - 01 - 01), pages 236 - 249, XP009107181, ISSN: 0075 - 4617, DOI: 10.1002 / JLAC.19375320120 discloses 4,5 - diiodo - 3 - methylthiophene - 2 - carboxylic acid. However, none of the above - mentioned prior - art compounds fall within the scope of the present invention because they are all excluded by the limiting conditions.

[0197] In one embodiment, R 1 is halogen, cyano, methyl or C1 - C2 - haloalkyl. In one embodiment, R 1 is halogen, cyano, methyl, trifluoromethyl or difluoromethyl. In one embodiment, R 1 is halogen, cyano or methyl. In one embodiment, R 1 is halogen or cyano. In one embodiment, R 1 is C1 - C2 - haloalkyl. In one embodiment, R 1 is trifluoromethyl or difluoromethyl.

[0198] In one embodiment, R 2 is halogen, cyano or C1 - C2 - haloalkyl. In one embodiment, R 2 is halogen, cyano, trifluoromethyl or difluoromethyl. In one embodiment, R 1 is halogen or cyano. In one embodiment, R 2 is C1 - C2 - haloalkyl. In one embodiment, R 2 is trifluoromethyl or difluoromethyl.

[0199] In one embodiment, R 3 is halogen, cyano, methyl or C1 - C2 - haloalkyl. In one embodiment, R 3 is halogen, cyano, methyl, trifluoromethyl or difluoromethyl. Compounds produced by combinations that violate the laws of nature are not included herein, and thus those skilled in the art will exclude them based on his / her expertise. For example, ring structures having three or more adjacent oxygen atoms are excluded.

[0200] Depending on the nature of the substituents, the compounds of formula (I) or (II) can exist in the form of different stereoisomers. These stereoisomers are, for example, enantiomers, diastereomers, atropisomers or geometric isomers. Accordingly, the present invention includes pure stereoisomers and any mixtures of these isomers. When a compound can exist in two or more tautomeric forms at equilibrium, the compound as referred to by the description of one tautomeric form is considered to include all tautomeric forms.

[0201] Depending on the number of double bonds in the compound, any compound of the present invention can also exist in the form of one or more geometric isomers. Geometric isomers of the nature of the substituents of the double bond or the ring can exist in the cis (=Z-) or trans (=E-) form. Accordingly, the present invention also relates to all geometric isomers and all possible mixtures in all ratios.

[0202] The compounds of formula (I) or (II) can suitably be in their free form, salt form, N-oxide form or solvate form (such as hydrate).

[0203] Depending on the nature of the substituents, the compounds of formula (I) or (II) can exist in the form of the free compound and / or its salts such as agrochemically active salts.

[0204] Agrochemically active salts include acid addition salts of inorganic acids and organic acids as well as salts of common bases. Examples of inorganic acids are hydrohalic acids such as hydrogen fluoride, hydrogen chloride, hydrogen bromide and hydrogen iodide; sulfuric acid; phosphoric acid and nitric acid; and acid salts such as sodium hydrogen sulfate and potassium hydrogen sulfate. Useful organic acids include, for example, formic acid, carbonic acid and alkanoic acids such as acetic acid, trifluoroacetic acid, trichloroacetic acid and propionic acid, as well as glycolic acid, thiocyanic acid, lactic acid, succinic acid, citric acid, benzoic acid, cinnamic acid, oxalic acid, saturated or mono- or di-unsaturated fatty acids having 6 to 20 carbon atoms, alkyl sulfuric acid monoesters, alkyl sulfonic acids (sulfonic acids of straight-chain or branched-chain alkyls having 1 to 20 carbon atoms), aryl sulfonic acids or aryl disulfonic acids (aryl groups carrying one or two sulfonic acid groups such as phenyl and naphthyl), alkyl phosphonic acids (phosphonic acids of straight-chain or branched-chain alkyls having 1 to 20 carbon atoms), aryl phosphonic acids or aryl diphosphonic acids (aryl groups carrying one or two phosphonic acid groups such as phenyl and naphthyl), wherein the alkyl and aryl groups can carry other substituents such as p-toluenesulfonic acid, salicylic acid, p-aminosalicylic acid, 2-phenoxybenzoic acid, 2-acetoxybenzoic acid, etc.

[0205] A solvate of a compound of formula (I) or (II) or its salt is a stoichiometric composition of the compound with a solvent.

[0206] The compounds of formula (I) or (II) can exist in a variety of crystalline and / or amorphous forms. Crystalline forms include non-solvated crystalline forms, solvates and hydrates.

[0207] Method for preparing the compound of formula (1)

[0208] The present invention relates to a method for preparing a compound of formula (I). The compound of formula (I) can be prepared by various routes similar to known methods (see the references therein), and by one or more of the following synthetic routes described below and in the experimental section.

[0209] Conventional synthetic route of the compound of formula (I)

[0210] Unless otherwise specified, hereinafter, R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、W, Y, Z and n have the same meanings as those given above for the compound of formula (I).

[0211] Method A1

[0212] The compound of formula (Ia) can be prepared by Method A1, which comprises the step of reacting one of the compounds of formula (III) or its salts with one of the compounds of formula (IV) or its salts, as shown in the following reaction scheme:

[0213]

[0214] Method A1

[0215] wherein U 1 is halogen, hydroxy or C1-C6-alkoxy.

[0216] When U 1When U represents a hydroxyl group, method A1 is advantageously carried out in the presence of a condensing agent. Suitable condensing agents can be selected from the non-limiting list consisting of: acyl halide formers such as phosgene, phosphorus tribromide, phosphorus trichloride, phosphorus pentachloride, phosphorus oxychloride, oxalyl chloride or thionyl chloride; acid anhydride formers such as ethyl chloroformate, methyl chloroformate, isopropyl chloroformate, isobutyl chloroformate or methanesulfonyl chloride; carbodiimides such as N,N'-dicyclohexylcarbodiimide (DCC), N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride (EDC) or other common condensing agents such as phosphorus pentoxide, polyphosphoric acid, bis(2-oxo-3-oxazolidinyl)phosphinic chloride, 1-[bis(dimethylamino)methylene]-1H-1,2,3-triazolo[4,5-b]pyridinium 3-oxide hexafluorophosphate (HATU), 2-(1H-benzotriazol-1-yl)-1,1,3,3-tetramethyluronium tetrafluoroborate (TBTU), (1-cyano-2-ethoxy-2-oxoethylideneaminooxy)dimethylamino-morpholino-carbenium hexafluorophosphate, N,N'-carbonyl-diimidazole, 2-ethoxy-N-ethoxycarbonyl-1,2-dihydroquinoline (EEDQ), triphenylphosphine / carbon tetrachloride, 4-(4,6-dimethoxy[1.3.5]-triazin-2-yl)-4-methylmorpholinium chloride hydrate, bis(2-oxo-3-oxazolidinyl)phosphinic chloride (BOP-Cl), tripyrrolidinylphosphonium bromide hexafluorophosphate (PyBroP), 2-chloro-1,3-dimethylimidazolium chloride (DMC) or propanephosphonic anhydride (T3P) and 3-(diethoxyphosphoryloxy)-1,2,3-benzotriazin-4(3H)-one (DEPBT).

[0217] When U 1 represents a halogen, method A1 is advantageously carried out in the presence of an acid binder. Suitable acid binders for carrying out method A1 are in each case all inorganic and organic bases commonly used for these reactions. Preferred are alkali metal carbonates such as cesium carbonate, sodium carbonate, potassium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate; alkaline earth metal acetates such as sodium acetate, potassium acetate, calcium acetate; and tertiary amines such as trimethylamine, triethylamine, diisopropylethylamine, tributylamine, N,N-dimethylaniline, N-methylpiperidine, N,N-dimethylpyridin-4-amine, 1,4-diazabicyclo[2.2.2]octane (DABCO), 1,5-diazabicyclo[4.3.0]non-5-ene (DBN) or 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU); or aromatic bases such as pyridine.

[0218] When U 1 represents a C1-C6-alkoxy group, method A1 can optionally be carried out with an excess of the amine component in the presence of a Lewis acid such as trimethylaluminum.

[0219] If appropriate, Method A1 can be carried out in the presence of a base and, if appropriate, in the presence of a solvent, preferably under anhydrous conditions.

[0220] There are no particular restrictions on the suitable solvents for carrying out Method A1. They can be common inert organic solvents as long as they do not dissolve the compound to react with it or exhibit any specific interaction with it. Optionally halogenated aliphatic, alicyclic or aromatic hydrocarbons are preferably used, such as petroleum ether, pentane, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, decalin, ISOPARTM E or ISOPARTM G; chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane or trichloroethane; ethers, such as diethyl ether, diisopropyl ether, methyl tert-butyl ether, methyl tert-amyl ether, dioxane, tetrahydrofuran, 2-methyltetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane or anisole; nitriles, such as acetonitrile, propionitrile, n-butyronitrile or isobutyronitrile or benzonitrile; amides, such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric triamide; ureas, such as 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone; esters, such as methyl acetate or ethyl acetate; sulfoxides, such as dimethyl sulfoxide; or sulfones, such as sulfolane; and mixtures thereof.

[0221] Method A1 can be carried out in an inert atmosphere such as an argon or nitrogen atmosphere. When carrying out Method A1, 1 mole or an excess of the compound of formula (VIII) and 1 to 5 moles of the base can be used per mole of the compound of formula (IV). Reaction components in other ratios can also be used. The post-treatment is carried out by known methods.

[0222] The compounds of formula (IV) are commercially available or can be prepared by well-known methods (J.Med.Chem.2018,61,8670 - 8692; Tetrahedron,44(1),195 - 202; 1988,WO2009070485; WO2019086142; Chem.Res.Toxicol.1990,3,118 - 124; JP49035334; JP49000223; Journal of OrganicChemistry(1989),54(12),2940 - 2949).

[0223] wherein U 1 The compounds of formula (IIIa) representing a hydroxyl group are commercially available or can be prepared from the compounds of formula (IIIb) wherein U1 represents a C1-C6-alkoxy group by well-known methods such as alkaline hydrolysis, or can be prepared by known methods (Beilstein J.Org.Chem.2007,3, issue 23).

[0224] Among them, U 1 The compound of formula (IIIc) representing a halogen is commercially available or can be prepared from the compound of formula (IIIa) in which U1 represents a hydroxyl group by well-known methods.

[0225] Among them, U 1 The compound of formula (IIIb) representing a C1-C6-alkoxy group can be prepared from the compound of formula (IIIa) in which U1 represents a hydroxyl group by well-known methods.

[0226] Method B1

[0227] Compounds of formula (Ib) (wherein R 1 is a C1-C6-alkyl group), (Ic) (wherein R 2 is a C1-C6-alkyl group) and (Id) (wherein R 3 is a C1-C6-alkyl group) can be prepared by method B1, which comprises the step of reacting one of the compounds of formula (Va), (Vb) or (Vc) or their salts with one of the compounds of formula (VIa), (VIb) or (VIc) or their salts, as shown in the following reaction scheme:

[0228]

[0229] Method B1

[0230] Among them, U 3 is a boron derivative, such as boric acid, a borate derivative, a potassium trifluoroborate derivative or a halogenated metal that can be complexed with 1 to 2 ligands, such as magnesium halide or zinc halide,

[0231] Wherein:

[0232] For (Va), U 2 is bromine, iodine, a mesylate group, a tosylate group or a trifluoromethanesulfonate group

[0233] The conditions are:

[0234] -R 1 or R 2 is not iodine

[0235] -When R 1 or R 2 is bromine, U 2 is not bromine

[0236] For (Vb), U 2 is bromine, iodine, a mesylate group, a tosylate group or a trifluoromethanesulfonate group

[0237] The conditions are:

[0238] -R 1 or R 3 is not iodine

[0239] - When R 1 or R 3 is bromine, U 2 is not bromine

[0240] For (Vc), U 2 is bromine, iodine, a mesylate group, a tosylate group or a triflate group

[0241] The conditions are as follows:

[0242] -R 2 or R 3 is not iodine

[0243] - When R 2 or R 3 is bromine, U 2 is not bromine.

[0244] Method B1 can be carried out in the presence of a transition metal catalyst such as palladium, if appropriate, in the presence of a phosphine ligand or an N-heterocyclic carbene ligand, if appropriate, in the presence of a base, and if appropriate in the presence of a solvent according to known methods (WO2012054721, Angew. Chem. Int. Ed. 2017, 56, 1581, Angew. Chem. Int. Ed. 2017, 56, 7078, and the references cited therein).

[0245] Method B1 can be carried out in the presence of a catalyst such as a metal salt or a complex. Suitable metal derivatives for this purpose are transition metal catalysts such as palladium. Suitable metal salts or complexes for this purpose are, for example, palladium chloride, palladium acetate, tetrakis(triphenylphosphine)palladium(0), bis(dibenzylideneacetone)palladium(0), tris(dibenzylideneacetone)dipalladium(0), bis(triphenylphosphine)palladium(II) dichloride, [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II), bis(cinnamyl)dichlorodipalladium(II), bis(allyl)-dichlorodipalladium(II), [1,1'-bis(di-tert-butylphosphino)ferrocene]dichloropalladium(II), di-μ-iodobis(tritert-butylphosphine)palladium(I) or di-μ-bromobis(tritert-butylphosphine)palladium(I).

[0246] The palladium complex can also be produced in the reaction mixture by separately adding a palladium salt and a ligand or salt such as triethylphosphine, tri-tert-butylphosphine, tri-tert-butylphosphine tetrafluoroborate, tricyclohexylphosphine, 2-(dicyclohexylphosphino)biphenyl, 2-(di-tert-butylphosphino)biphenyl, 2-(dicyclohexylphosphino)-2'-(N,N-dimethylamino)biphenyl, 2-(tert-butylphosphino)-2'-(N,N-dimethylamino)biphenyl, 2-di-tert-butylphosphino-2',4',6'-triisopropylbiphenyl, 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl, 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl, 2-dicyclohexylphosphino-2,6'-dimethoxybiphenyl, 2-dicyclohexylphosphino-2',6'-diisopropoxybiphenyl, triphenylphosphine, tri-(o-toluene)biphenyl, or tri-(tri-)-phenylphosphine. 1,1'-bis(diphenylphosphino)-2'-(N,N-dimethylamino)-biphenyl, 1,1'-bis(diphenylphosphino)-ferrocene, (R)-(-)-1-[(S)-2-diphenylphosphino)ferrocenyl]ethyldicyclohexylphosphine, tris-(2,4-tert-butylphenyl)phosphite, di(1-adamantyl)-2-morpholinylphenylphosphine or 1,3-bis(2,4,6-trimethylphenyl)imidazolium chloride.

[0247] It is also advantageous to select suitable catalysts and / or ligands from commercial catalogues, such as "Metal Catalysts for Organic Synthesis" by Strem Chemicals or "Phosphorous Ligands and Compounds" by Strem Chemicals.

[0248] Suitable bases for carrying out Method B1 can be inorganic and organic bases commonly used in these reactions. It is preferred to use alkaline earth metal or alkali metal hydroxides such as sodium hydroxide, calcium hydroxide, potassium hydroxide or other ammonium hydroxide derivatives; alkaline earth metal, alkali metal or ammonium fluorides such as potassium fluoride, cesium fluoride or tetrabutylammonium fluoride; alkaline earth metal or alkali metal carbonates such as sodium carbonate, potassium carbonate, potassium bicarbonate, sodium bicarbonate or cesium carbonate; alkali metal or alkaline earth metal acetates such as sodium acetate, lithium acetate, potassium acetate or calcium acetate; alkali metal or alkaline earth metal phosphates such as tripotassium phosphate; alkali metal alkoxides such as potassium tert-butoxide or sodium tert-butoxide; tertiary amines such as trimethylamine, triethylamine, tributylamine, N,N-dimethylaniline, N,N-dicyclohexylmethylamine, N,N-diisopropylethylamine, N-methylpiperidine, N,N-dimethylaminopyridine, 1,4-diazabicyclo[2.2.2]octane (DABCO), 1,5-diazabicyclo[4.3.0]non-5-ene (DBN) or 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU); and aromatic bases such as pyridine, methylpyridine, dimethylpyridine or trimethylpyridine.

[0249] Suitable solvents for carrying out Method B1 can be common inert organic solvents. It is preferred to use optionally halogenated aliphatic, alicyclic or aromatic hydrocarbons such as petroleum ether, pentane, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin; chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane or trichloroethane; ethers such as diethyl ether, diisopropyl ether, methyl tert-butyl ether, methyl tert-amyl ether, dioxane, tetrahydrofuran, 2-methyltetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane or anisole; nitriles such as acetonitrile, propionitrile, n-butyronitrile or isobutyronitrile or benzonitrile; amides such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric triamide; ureas such as 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone; esters such as methyl acetate or ethyl acetate; sulfoxides such as dimethyl sulfoxide; or sulfones such as sulfolane; and mixtures thereof.

[0250] It can also be advantageous to use a cosolvent such as water or an alcohol for Method B1, and the alcohol is for example methanol, ethanol, propanol, isopropanol or tert-butanol.

[0251] Method B1 can be carried out in an inert atmosphere such as an argon or nitrogen atmosphere. When carrying out Method B1, 1 mole or an excess of the compound of formula (VIa), (VIb) or (VIc) and 1 to 5 moles of the base and 0.01 to 20 mol% of the palladium complex can be used per mole of the compound of formula (Va), (Vb) or (Vc). Other ratios of reaction components can also be used. The post-treatment is carried out by known methods.

[0252] The compounds of formula (VIa), (VIb) or (VIc) are commercially available or can be prepared by well-known methods.

[0253] The compound of formula (Va), (Vb) or (Vc) in which W is oxygen can be prepared by reacting a compound of formula (VIIa), (VIIb) or (VIIc) with a compound of formula (IV) under the conditions described in Method A1:

[0254]

[0255] wherein U 2 and U 1 as defined herein.

[0256] The compound of formula (VIIa), (VIIb) or (VIIc) in which U 2 is chlorine, bromine or iodine is commercially available or can be prepared by well-known methods using reaction conditions similar to those disclosed for the preparation of the compound of formula (III).

[0257] The compound of formula (VIIa), (VIIb) or (VIIc) in which U 2 is a mesylate group, a tosylate group or a triflate group can be prepared from the corresponding compound having a hydroxyl group at the U 2 position by a known method.

[0258] Method C1

[0259] The compound of formula (Ie) can be prepared from the compound of formula (Ia) by a sulfidation reaction in Method C1, as shown in the following reaction scheme:

[0260]

[0261] Method C1

[0262] The Method C1 of the present invention is carried out in the presence of a sulfiding agent.

[0263] Suitable sulfurizing agents for carrying out Method C1 of the present invention may be sulfur (S), hydrogen sulfide (H₂S), sodium sulfide (Na₂S), sodium hydrosulfide (NaHS), boron trisulfide (B₂S₃), bis(diethylaluminum) sulfide ((AlEt₂)₂S), ammonium sulfide ((NH₄)₂S), phosphorus pentasulfide (P₂S₅), Lawesson's reagent (2,4-bis(4-methoxyphenyl)-1,2,3,4-dithiadiphosphetane 2,4-disulfide), or a polymer-supported thionating reagent as described, for example, in Journal of the Chemical Society, Perkin 1 (2001), 358, and optionally present catalytic or stoichiometric or excess bases such as inorganic and organic bases. Alkali metal carbonates such as sodium carbonate, potassium carbonate, potassium bicarbonate, sodium bicarbonate are preferably used; heterocyclic aromatic bases such as pyridine, methylpyridine, dimethylpyridine, trimethylpyridine; and tertiary amines such as trimethylamine, triethylamine, tributylamine, N,N-dimethylaniline, N,N-dimethylpyridin-4-amine or N-methyl-piperidine.

[0264] Suitable solvents for carrying out Method C1 of the present invention may be common inert organic solvents. Optionally halogenated aliphatic, cycloaliphatic or aromatic hydrocarbons such as petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin, chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane or trichloroethane are preferably used, ethers such as diethyl ether, diisopropyl ether, methyl tert-butyl ether, methyl tert-amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane or 1,2-diethoxyethane, nitriles such as acetonitrile, propionitrile, n- or isobutyronitrile or benzonitrile, sulfur-containing solvents such as sulfolane or carbon disulfide.

[0265] When carrying out Method C1 of the present invention, 1 mole or an excess of sulfur equivalent of the sulfurizing agent and 1 to 3 moles of the base may be used per mole of the amide reactant (Ia).

[0266] Other ratios of the reaction components may also be used. Work-up is carried out by known methods.

[0267] Method D1

[0268] Formula (If) (wherein R 1 is cyano), (Ig) (wherein R 2 is cyano) and (Ih) (wherein R 3Compounds having a cyano group can be prepared by Method D1, which comprises the step of reacting one of the compounds of formula (Va), (Vb) or (Vc) or its salt with a cyanating reagent according to a known method (Chem. Rev. 1987, 87, 4, 779-794; Chem. Soc. Rev., 2011, 40, 5049-5067; WO2012123471 and the references cited therein).

[0269] Method D1 can be carried out in the presence of a transition metal catalyst such as a metal salt or complex, and if appropriate, in the presence of a ligand; if appropriate, in the presence of a base, and if appropriate in the presence of a solvent. Suitable metal derivatives for this purpose are transition metals such as palladium or copper. Suitable solvents for carrying out Method D1 are not particularly limited. They can be common inert organic solvents as long as they do not dissolve the compound to react with it or exhibit any specific interaction with it. Suitable solvents can be, for example, the solvents disclosed in Method A1. Examples of cyanating agents include potassium ferrocyanide, copper cyanide, zinc cyanide, sodium cyanide, potassium cyanide.

[0270] Method E1

[0271] The compound of formula (I) as defined herein can be prepared from one of the compounds of formula (VIII) or its salt by carrying out a halogenation reaction by Method E1, as shown in the following reaction scheme:

[0272]

[0273] Method E1

[0274] wherein U 4 、U 5 and U 6 are independently selected from hydrogen, halogen, cyano, C1-C6-alkyl or C1-C6-haloalkyl, provided that at least one of U 4 、U 5 or U 6 is hydrogen.

[0275] Method E1 can be carried out according to known methods (Angewandte Chemie, International Edition, 52(16), 4440 - 4444; 2013; ACS Catalysis, 6(11), 7839 - 7843; 2016; Journal of the American Chemical Society, 2017, 139, 888; Angewandte Chemie, International Edition, 2014, 53, 7928; Journal of the American Chemical Society, 2018, 140, 2789; WO2008156879; WO2012114285; WO2008109786; WO2007098356).

[0276] Method E1 is carried out in the presence of a halogenating agent and, if appropriate, in the presence of a solvent.

[0277] Suitable halogenating agents for carrying out Method E1 are not particularly limited as long as they can be used for bromination, chlorination, iodination or fluorination. Examples of brominating agents include bromine, N - bromosuccinimide, 1,2 - dibromotetrachloroethane and 1,3 - dibromo - 5,5 - dimethyl - 2,4 - imidazolidinedione. Examples of chlorinating agents include N - chlorosuccinimide, hexachloroethane, sulfuryl chloride and 1,3 - dichloro - 5,5 - dimethyl - 2,4 - imidazolidinedione. Examples of iodinating agents include iodine, N - iodosuccinimide, iodine monochloride and 1,3 - diiodo - 5,5 - dimethyl - 2,4 - imidazolidinedione. Examples of fluorinating agents include N - fluorobenzenesulfonimide and 1 - chloromethyl - 4 - fluoro - 1,4 - diazabicyclo[2.2.2]octane bis(tetrafluoroborate).

[0278] Suitable solvents for carrying out method E1 are not particularly limited. They may be common inert organic solvents, provided that they do not dissolve the compound to react with it or exhibit any specific interaction with it. Suitable solvents may be, for example, the solvents disclosed in combination with method A1. For carrying out method E1, it is also advantageous to use an organic acid such as acetic acid or trifluoroacetic acid as a solvent or co-solvent. For carrying out method E1, it is also advantageous to use a Lewis acid such as zinc(II) chloride as a catalyst. For carrying out method E1, it is also advantageous to use a transition metal catalyst such as a palladium catalyst. For carrying out method E1, it is also advantageous to use a suitable organometallic reagent such as n-butyllithium. For carrying out method E1, according to a known method (WO2020079205), it is also advantageous to use a suitable base before halogenation, such as n-butyllithium, lithium diisopropylamide, lithium tetramethylpiperidide, lithium bis(trimethylsilyl)amide, methyllithium or chloro-(2,2,6,6-tetramethyl-1-piperidyl)magnesium, etc., preferably carried out under anhydrous conditions. Optionally, lithium chloride can be used in combination with these reagents preformed.

[0279] Method F1

[0280] A compound of formula (Ii) as defined herein (wherein R 3 is halogen, cyano, C1-C6-alkyl or C1-C6-haloalkyl) can be prepared by method F1, which comprises the step of diazotizing one of the compounds of formula (IX) or its salts, followed by aromatic substitution to provide a compound of formula (Ii), as shown in the following reaction scheme:

[0281]

[0282] Method F1

[0283] wherein U 7 , U 8 and U 9 are independently selected from amino, halogen, cyano, C1-C6-alkyl or C1-C6-haloalkyl, provided that at least one of U 7 , U 8 or U 9 is amino.

[0284] Method F1 can be carried out according to a known method (The Chemistry of diazonium and diazo groups; Saul Patai; Wiley-Interscience; 1978; pages 288-280 and 645-657; Account of Chemical Research (2018), 51, 496 and the references cited therein).

[0285] One of the compounds of formula (IX) or a salt thereof as defined herein can be prepared by the following method, which comprises a step of reducing a nitro group according to a known method (Science of Synthesis: Catalytic Reduction in Organic Synthesis 2; J.G. de Vries, 2018, Chapter 2.7: Reduction of Nitro Compounds to Amines, Azo Compounds, Hydroxylamines, and Oximes, and Reduction of N-Oxides to Amines, and the references therein) or deprotecting a protected amino group according to a known method.

[0286] Examples of protecting groups for an amino group include benzyl, 4-methoxybenzyl, allyl, unsubstituted or substituted C1-C6-alkylsulfonyl, trifluoromethylsulfonyl, unsubstituted or substituted phenylsulfonyl, unsubstituted or substituted C1-C6-alkoxycarbonyl, unsubstituted or substituted benzyloxycarbonyl, allyloxycarbonyl, acetyl or trifluoroacetyl.

[0287] The deprotection process can be carried out according to known methods for removing protecting groups (Greene’s Protective Groups in Organic Synthesis; Peter G.M. Wuts; Wiley; Fifth Edition; 2014; 895-1194). For example, tert-butoxycarbonyl and benzyloxycarbonyl protecting groups can be removed in an acidic medium (e.g., with hydrochloric acid or trifluoroacetic acid). The benzyl protecting group can be removed by hydrogenolysis with hydrogen in the presence of a catalyst (e.g., palladium on activated carbon). Trifluoroacetyl can be removed in a basic medium (e.g., with potassium carbonate or lithium hydroxide).

[0288] A compound of formula (Ij), wherein Z is -C(=O)-OR a , wherein R a is selected from C1-C6-alkyl; C1-C6-haloalkyl; C1-C6-cyanoalkyl; C2-C6-alkenyl; C2-C6-alkynyl; C3-C8-cycloalkyl; aryl; aralkyl; 4-, 5- or 6-membered non-aromatic heterocyclic group; -C1-C6-alkyl-Si(C1-C6-alkyl)3; -C1-C6-alkyl-C3-C8-cycloalkyl; 5- to 9-membered heteroaryl and -C1-C6-alkyl-5- to 9-membered heteroaryl, and the compound of formula (Ij) can be prepared from a compound of formula (Ik) (wherein Z is -C(=O)-OR a , wherein R ais prepared by known coupling methods of hydrogen and the corresponding alcohol or one of their salts under the conditions described in Binding Method A1.

[0289] The compound of formula (Ik) wherein Z is -C(=O)-OR a , wherein R a is hydrogen) can be prepared from the compound of formula (Ij) by known methods such as hydrolysis, in which formula (Ij) Z is -C(=O)-OR a , wherein R a is selected from C1-C6-alkyl; C1-C6-haloalkyl; C1-C6-cyanoalkyl; C2-C6-alkenyl; C2-C6-alkynyl; C3-C8-cycloalkyl; aryl; aralkyl; 4-, 5- or 6-membered non-aromatic heterocyclic group; -C1-C6-alkyl-Si(C1-C6-alkyl)3; -C1-C6-alkyl-C3-C8-cycloalkyl; 5- to 9-membered heteroaryl and -C1-C6-alkyl-5- to 9-membered heteroaryl. Examples of hydrolysis reagents include lithium hydroxide, potassium hydroxide, sodium hydroxide, trimethyltin hydroxide. Hydrolysis can be carried out as described in WO2008157844; WO2006002099; WO20050256107; Angewandte Chemie, International Edition (2005), 44(9), 1378-1382.

[0290] The compound of formula (Im) wherein Z is -C(=O)-SR a , -C(=O)-NR b R c or -C(=O)-NH-CR d R e -C(=O)-OR a ) can be prepared from the compound of formula (Ik) wherein Z is -C(=O)-OR a , wherein R a is hydrogen and the corresponding thiol, amine) or one of their salts by known coupling methods under the conditions described in Binding Method A1.

[0291] Method for preparing the compound of formula (II)

[0292] The present invention relates to a method for preparing a compound of formula (II). The compound of formula (II) can be prepared by various routes similar to known methods (see the references therein), and by one or more of the following synthetic routes described below and in the experimental section.

[0293] Conventional synthetic route of the compound of formula (II)

[0294] The present invention relates to a method for preparing a compound of formula (II). The compound of formula (II) can be prepared by various routes similar to those described in the following known methods: Beilstein Journal of Organic Chemistry (2007), 3, No. 23; WO2008109786; Justus Liebigs Annalen der Chemie (1937), 532, 236-49; Justus Liebigs Annalen der Chemie (1938), 536, 135-42; WO2017212010; WO2012021696; WO2003024961; Tetrahedron Letters (1997), 38(6), 1049-1052; WO200302496; Journal of Agriculture and Food Chemistry (2007), 55(18), 7517-7526, WO2020079205 and other references therein, or by one or more of the following synthetic routes described below and in the experimental section.

[0295] The compound of formula (II) can be prepared by successively applying the following methods in various orders by various routes.

[0296] Unless otherwise specified, hereinafter, R 1 、R 2 、R 3 and A have the same meanings as those given above for the compound of formula (II).

[0297] Method A2

[0298] The compound of formula (IIa), wherein R 1 is C1-C3-alkyl, (IIb), wherein R 2 is C1-C3-alkyl and (IIc), wherein R 3 is C1-C3-alkyl, can be prepared by method A2, which method A2 comprises the step of reacting one of the compounds of formula (Xa), (Xb) or (Xc) or a salt thereof with one of the compounds of formula (VIa), (VIb) or (VIc) or a salt thereof, as shown in the following reaction scheme:

[0299]

[0300] Method A2

[0301] wherein U 3is a boron derivative, such as boric acid, borate ester derivative, potassium trifluoroborate derivative or a halogenated metal that can be complexed by 1 to 2 ligands, such as halogenated magnesium or halogenated zinc,

[0302] wherein:

[0303] For (Xa), U 2 is bromine, iodine, a mesylate group, a tosylate group or a trifluoromethanesulfonate group

[0304] provided that:

[0305] -R 1 or R 2 is not iodine

[0306] -When R 1 or R 2 is bromine, U 2 is not bromine

[0307] For (Xb), U 2 is bromine, iodine, a mesylate group, a tosylate group or a trifluoromethanesulfonate group

[0308] provided that:

[0309] -R 1 or R 3 is not iodine

[0310] -When R 1 or R 3 is bromine, U 2 is not bromine

[0311] For (Xc), U 2 is bromine, iodine, a mesylate group, a tosylate group or a trifluoromethanesulfonate group

[0312] provided that:

[0313] -R 2 or R 3 is not iodine

[0314] -When R 2 or R 3 is bromine, U 2 is not bromine.

[0315] Method A2 can be carried out in the presence of a transition metal catalyst such as palladium, if appropriate, in the presence of a phosphine ligand or an N-heterocyclic carbene ligand, if appropriate, in the presence of a base, if appropriate in the presence of a solvent according to known methods (WO2012054721, Angew. Chem. Int. Ed. 2017, 56, 1581, Angew. Chem. Int. Ed. 2017, 56, 7078, and the references cited therein).

[0316] Method A2 can be carried out in the presence of a catalyst such as a metal salt or a complex. Suitable metal derivatives for this purpose are transition metal catalysts, such as palladium. Suitable metal salts or complexes for this purpose are, for example, palladium chloride, palladium acetate, tetrakis(triphenylphosphine)palladium(0), bis(dibenzylideneacetone)palladium(0), tris(dibenzylideneacetone)dipalladium(0), bis(triphenylphosphine)palladium(II)dichloride, [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II), bis(cinnamyl)dichlorodipalladium(II), bis(allyl)-dichlorodipalladium(II), [1,1'-bis(di-tert-butylphosphino)ferrocene]dichloropalladium(II), di-μ-iodobis(tri-tert-butylphosphino)dipalladium(I) or di-μ-bromobis(tri-tert-butylphosphino)dipalladium(I).

[0317] The palladium complex can also be produced in the reaction mixture by separately adding a palladium salt and a ligand or salt such as triethylphosphine, tri-tert-butylphosphine, tri-tert-butylphosphine tetrafluoroborate, tricyclohexylphosphine, 2-(dicyclohexylphosphino)biphenyl, 2-(di-tert-butylphosphino)biphenyl, 2-(dicyclohexylphosphino)-2'-(N,N-dimethylamino)biphenyl, 2-(tert-butylphosphino)-2'-(N,N-dimethylamino)biphenyl, 2-di-tert-butylphosphino-2',4',6'-triisopropylbiphenyl, 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl, 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl, 2-dicyclohexylphosphino-2,6'-dimethoxybiphenyl, 2-dicyclohexylphosphino-2',6'-diisopropoxybiphenyl, triphenylphosphine, tri-(o-toluene)biphenyl, or tri-(tri-)-phenylphosphine. 1,1'-bis(diphenylphosphino)-2'-(N,N-dimethylamino)-biphenyl, 1,1'-bis(diphenylphosphino)-ferrocene, (R)-(-)-1-[(S)-2-diphenylphosphino)ferrocenyl]ethyldicyclohexylphosphine, tris-(2,4-tert-butylphenyl)phosphite, di(1-adamantyl)-2-morpholinylphenylphosphine or 1,3-bis(2,4,6-trimethylphenyl)imidazolium chloride.

[0318] Also advantageously, a suitable catalyst and / or ligand is selected from a commercial catalog, such as "Metal Catalysts for Organic Synthesis" by Strem Chemicals or "Phosphorous Ligands and Compounds" by Strem Chemicals.

[0319] Suitable bases for carrying out Method A2 Suitable bases can be inorganic and organic bases commonly used in these reactions. Preferably, alkaline earth metal or alkali metal hydroxides are used, such as sodium hydroxide, calcium hydroxide, potassium hydroxide or other ammonium hydroxide derivatives; alkaline earth metal, alkali metal or ammonium fluorides, such as potassium fluoride, cesium fluoride or tetrabutylammonium fluoride; alkaline earth metal or alkali metal carbonates, such as sodium carbonate, potassium carbonate, potassium bicarbonate, sodium bicarbonate or cesium carbonate; alkali metal or alkaline earth metal acetates, such as sodium acetate, lithium acetate, potassium acetate or calcium acetate; alkali metal or alkaline earth metal phosphates, such as tripotassium phosphate; alkali metal alkoxides, such as potassium tert-butoxide or sodium tert-butoxide; tertiary amines, such as trimethylamine, triethylamine, tributylamine, N,N-dimethylaniline, N,N-dicyclohexylmethylamine, N,N-diisopropylethylamine, N-methylpiperidine, N,N-dimethylaminopyridine, 1,4-diazabicyclo[2.2.2]octane (DABCO), 1,5-diazabicyclo[4.3.0]non-5-ene (DBN) or 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU); and aromatic bases, such as pyridine, methylpyridine, dimethylpyridine or trimethylpyridine.

[0320] Suitable solvents for carrying out Method A2 can be common inert organic solvents. Preferably, optionally halogenated aliphatic, cycloaliphatic or aromatic hydrocarbons are used, such as petroleum ether, pentane, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin; chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane or trichloroethane; ethers, such as diethyl ether, diisopropyl ether, methyl tert-butyl ether, methyl tert-amyl ether, dioxane, tetrahydrofuran, 2-methyltetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane or anisole; nitriles, such as acetonitrile, propionitrile, n-butylnitrile or isobutylnitrile or benzonitrile; amides, such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric triamide; ureas, such as 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone; esters, such as methyl acetate or ethyl acetate; sulfoxides, such as dimethyl sulfoxide; or sulfones, such as sulfolane; and mixtures thereof.

[0321] It can also be advantageous to use a cosolvent such as water or an alcohol for Method A2, and the alcohol is, for example, methanol, ethanol, propanol, isopropanol or tert-butanol.

[0322] Method A2 can be carried out in an inert atmosphere such as an argon or nitrogen atmosphere. When carrying out Method A, 1 mole or an excess of the compound of formula (VIa), (VIb) or (VIc) and 1 to 5 moles of base and 0.01 to 20 mole % of palladium complex can be used per mole of the compound of (Xa), (Xb) or (Vc). Other ratios of reaction components can also be used. The work-up is carried out by known methods.

[0323] The compounds of formula (VIa), (VIb) or (VIc) are commercially available or can be prepared by well-known methods.

[0324] The compounds of formula (Xa), (Xb) or (Xc) are commercially available or can be prepared by well-known methods.

[0325] Method B2

[0326] The compounds of formula (IId) (wherein R 1 is cyano), (IIe) (wherein R 2 is cyano) and (IIf) (wherein R 3 is cyano) can be prepared by Method B2, which comprises the step of reacting a compound of formula (Xa), (Xb) or (Xc) or one of its salts with a cyanating reagent according to known methods (Chem. Rev. 1987, 87, 4, 779 - 794; Chem. Soc. Rev., 2011, 40, 5049 - 5067; WO2012123471 and the references cited therein).

[0327] Method B2 can be carried out in the presence of a transition metal catalyst such as a metal salt or complex and, if appropriate, in the presence of a ligand; if appropriate, in the presence of a base and if appropriate, in the presence of a solvent. Suitable metal derivatives for this purpose are transition metals such as palladium or copper. The suitable solvents for carrying out Method B2 are not particularly limited. They can be common inert organic solvents as long as they do not dissolve the compound to react with it or exhibit any specific interaction with it. Suitable solvents can be, for example, the solvents disclosed in connection with Method A2. Examples of cyanating agents include potassium ferrocyanide, copper cyanide, zinc cyanide, sodium cyanide, potassium cyanide.

[0328] Method C2

[0329] The compounds of formula (II) as defined herein can be prepared from a compound of formula (XI) or one of its salts by carrying out a halogenation reaction by Method C2, as shown in the following reaction scheme:

[0330]

[0331] Method C2

[0332] wherein U 4 、U 5 and U 6 are independently selected from hydrogen, halogen, cyano, C1-C3-alkyl or C1-C3-haloalkyl, provided that at least one of U 4 、U 5 or U 6 is hydrogen.

[0333] Method C2 can be carried out according to known methods (Angewandte Chemie, International Edition, 52(16), 4440-4444; 2013; ACS Catalysis, 6(11), 7839-7843; 2016; Journal of the American Chemical Society, 2017, 139, 888; Angewandte Chemie, International Edition, 2014, 53, 7928; Journal of the American Chemical Society, 2018, 140, 2789; WO2008156879; WO2012114285; WO2008109786; WO2007098356).

[0334] Method C2 is carried out in the presence of a halogenating agent and, if appropriate, in the presence of a solvent.

[0335] Suitable halogenating agents for carrying out Method C2 are not particularly limited as long as they can be used for bromination, chlorination, iodination or fluorination. Examples of brominating agents include bromine, N-bromosuccinimide, 1,2-dibromotetrachloroethane and 1,3-dibromo-5,5-dimethyl-2,4-imidazolidinedione. Examples of chlorinating agents include N-chlorosuccinimide, thionyl chloride, hexachloroethane and 1,3-dichloro-5,5-dimethyl-2,4-imidazolidinedione. Examples of iodinating agents include iodine, N-iodosuccinimide, iodine monochloride and 1,3-diiodo-5,5-dimethyl-2,4-imidazolidinedione. Examples of fluorinating agents include N-fluorobenzenesulfonimide and 1-chloromethyl-4-fluoro-1,4-diazabicyclo[2.2.2]octane bis(tetrafluoroborate).

[0336] There are no particular restrictions on the suitable solvents for carrying out Method C2. They can be common inert organic solvents, provided that they do not dissolve the compound to react with it or exhibit any specific interaction with it. Suitable solvents can be, for example, the solvents disclosed in combination with Method A2. For carrying out Method C2, it is also advantageous to use organic acids such as acetic acid or trifluoroacetic acid as solvents or co-solvents. For carrying out Method C2, it is also advantageous to use Lewis acids such as zinc(II) chloride as catalysts. For carrying out Method C2, it is also advantageous to use transition metal catalysts such as palladium catalysts.

[0337] For carrying out Method C2, it is also advantageous to use suitable organometallic reagents such as n-butyllithium. For carrying out Method C2, according to a known method (WO2020079205), it is also advantageous to use a suitable base before halogenation, such as n-butyllithium, lithium diisopropylamide, lithium tetramethylpiperidide, lithium bis(trimethylsilyl)amide, methyllithium or chloro-(2,2,6,6-tetramethyl-1-piperidyl)magnesium, etc., preferably under anhydrous conditions. Optionally, lithium chloride can be used in combination with these reagents pre-formed.

[0338] Method D2

[0339] The compound of formula (II) as defined herein can be prepared by Method D2, which comprises the steps of diazotizing one of the compounds of formula (XII) or its salts and then carrying out an aromatic substitution to provide the compound of formula (II), as shown in the following reaction scheme:

[0340]

[0341] Method D2

[0342] wherein U 7 、U 8 and U 9 are independently selected from amino, halogen, cyano, C1-C3-alkyl or C1-C3-haloalkyl, provided that at least one of U 7 、U 8 or U 9 is amino.

[0343] Method D2 can be carried out according to known methods (The Chemistry of diazonium and diazo groups; Saul Patai; Wiley-Interscience; 1978; pages 288 - 280 and 645 - 657; Account of Chemical Research (2018), 51, 496 and the cited references; Journal of Medicinal Chemistry, 46(18), 3914 - 3929; 2003; WO2012123471; Bioorganic & Medicinal Chemistry, 15(5), 2127 - 2146; 2007; WO2016092556; Advanced Synthesis & Catalysis, 356(10), 2343 - 2348; 2014).

[0344] One of the compounds of formula (XII) or a salt thereof as defined herein can be prepared by the following method, which method comprises a step of reducing a nitro group according to known methods (Science of Synthesis: Catalytic Reduction in Organic Synthesis 2; J.G. de Vries, 2018, Chapter 2.7: Reduction of Nitro Compounds to Amines, Azo Compounds, Hydroxylamines, and Oximes, and Reduction of N - Oxides to Amines, and the references therein) or deprotecting a protected amino group according to known methods.

[0345] Examples of amino - protecting groups include benzyl, 4 - methoxybenzyl, allyl, unsubstituted or substituted C1 - C6 - alkylsulfonyl, trifluoromethylsulfonyl, unsubstituted or substituted phenylsulfonyl, unsubstituted or substituted C1 - C6 - alkoxycarbonyl, unsubstituted or substituted benzyloxycarbonyl, allyloxycarbonyl, acetyl or trifluoroacetyl.

[0346] The deprotection process can be carried out according to known methods for removing protecting groups (Greene’s Protective Groups in Organic Synthesis; Peter G.M. Wuts; Wiley; 5th Edition; 2014; 895 - 1194). For example, tert - butyloxycarbonyl and benzyloxycarbonyl protecting groups can be removed in acidic media (e.g., with hydrochloric acid or trifluoroacetic acid). The benzyl protecting group can be removed by hydrogenolysis with hydrogen in the presence of a catalyst (e.g., palladium on activated carbon). Trifluoroacetyl groups can be removed in basic media (e.g., with potassium carbonate or lithium hydroxide).

[0347] Method E2

[0348] Compounds of formula (IIg) as defined herein (wherein R 1 、R 2 or R 3 are at least C1 - C3 - difluoroalkyl or C1 - C3 - fluoroalkyl, respectively) can be prepared by method E2, which comprises the step of fluorinating the corresponding compound (XIII) as shown in the following reaction scheme:

[0349]

[0350] Method E2

[0351] wherein U 10 、U 11 and U 12 are each independently selected from C1 - C3 - oxoalkylalkyl or C1 - C3 - hydroxyalkyl, halogen, cyano, C1 - C3 - alkyl or C1 - C3 - haloalkyl, provided that at least one of the corresponding U 10 、U 11 or U 12 is at least C1 - C3 - oxoalkylalkyl or C1 - C3 - hydroxyalkyl, respectively.

[0352] Suitable fluorinating agents for carrying out method E2 are not particularly limited as long as they can be used for fluorination. Examples of fluorinating agents include sulfur fluorides such as sulfur tetrafluoride, diethylaminosulfur trifluoride, morpholine sulfur trifluoride, bis(2 - methoxyethyl)aminosulfur trifluoride or 4 - tert - butyl - 2,6 - dimethylphenylsulfur trifluoride,

[0353] Method E2 can be carried out as described in WO1998042347; WO2015005489; European Journal of Medicinal Chemistry, 159, 23 - 34; 2018.

[0354] Method F2

[0355] The compound of formula (II) as defined herein can be prepared by method E2, which method E2 includes the step of hydrolysis from compound (XIV), as shown in the following reaction scheme:

[0356]

[0357] Method F2

[0358] Method F2 can be carried out as described in the following documents and the references therein: WO2006086488; WO2013170112; WO2000021928; J. Org. Chem. 2019, 84, 16, 9869 - 9896; Comprehensive Organic Functional Group Transformations, Volume 5, 1995, Chapter 5.02.1.2, Carbonation of Organometallic Reagents, 27 - 28.

[0359] Method G2

[0360] The compound of formula (IIh) as defined herein (provided that R 1 , R 2 and R 3 are not cyano) can be prepared by method G2, which method includes the hydrolysis step of the corresponding compound (XV) as shown in the following reaction scheme:

[0361]

[0362] Method F2

[0363] Method G2 can be carried out as described in Beilstein Journal of Organic Chemistry, 3, No. 23, 2007; WO2012075678.

[0364] The compound of formula (XV) is known or can be prepared by known methods.

[0365] The compound of formula (IIi) wherein A is hydrogen can be prepared from the compound of formula (IIj) wherein A is C1-C6-alkyl by known methods such as hydrolysis. Examples of hydrolysis reagents include lithium hydroxide, potassium hydroxide, sodium hydroxide, trimethyltin hydroxide. The hydrolysis can be carried out as described in WO2015043364, WO2017212010, WO2014140078, WO2003024961, WO2009154741, Angewandte Chemie, International Edition (2005), 44(9), 1378-1382.

[0366] The compound of formula (IIj) wherein A is C1-C6 alkyl can be prepared from the compound of formula (IIi) wherein A is hydrogen by known methods such as esterification. Such methods can be carried out as described in WO2015043364; WO2017212010; WO2014140078; WO2003024961; WO2009154741; Angewandte Chemie, International Edition (2005), 44(9), 1378-1382.

[0367] Method H2

[0368] The compound of formula (IIi) as defined herein can be prepared by process H2 which comprises the step of reacting a compound (XVI) as defined herein (wherein M represents an alkali metal (such as lithium) which may be complexed with 1 to 2 ligands or magnesium halide which may be complexed with 1 to 2 ligands) with carbon dioxide as shown in the following reaction scheme:

[0369]

[0370] Process H2

[0371] Method I2

[0372] The compound of formula (XVI) as defined herein can be prepared by process H2 which comprises a metallization step of a compound (XVII) wherein U 13 is selected from chlorine, bromine or iodine as shown in the following reaction scheme:

[0373]

[0374] Process G2

[0375] Method I2 can be prepared using magnesium metal or lithium metal, or using an organolithium reagent or a Grignard reagent or a prepared complex (prepared from an organolithium reagent or a Grignard reagent), preferably by halogen / metal exchange under anhydrous conditions. Optionally, lithium chloride can be used in combination with these reagents in a pre-formed form.

[0376] Method I2 can be carried out as described in WO2019209759; Angewandte Chemie, International Edition, 58(45), 16210 - 16216; 2019; New Journal of Chemistry, 41(19), 10929 - 10934, 2017; CN106518840; WO2014090918 or WO2013089087 and their references.

[0377] Examples of organolithium reagents used in the lithiation method include methyllithium, phenyllithium, n-butyllithium, sec-butyllithium, isobutyllithium, tert-butyllithium, etc.

[0378] Examples of Grignard reagents used in the magnesium complexation method include methylmagnesium chloride, ethylmagnesium chloride, n-butylmagnesium chloride, isopropylmagnesium chloride, chloro-(2,2,6,6-tetramethyl-1-piperidyl)magnesium, etc. A complex prepared from n-butylmagnesium chloride and n-butyllithium can also be used.

[0379] Examples of ligands used in the lithiation method or the magnesium complexation method include tetramethylethylenediamine, hexamethylphosphoric triamide, (+) or (-)-sparteine, or 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone.

[0380] The solvent used in the lithiation or magnesium complexation is not particularly limited as long as it forms an anhydrous reaction system without dissolving the compound to react with it or showing any specific interaction with it. Preferably, non-halogenated aliphatic, alicyclic or aromatic hydrocarbons are used, such as petroleum ether, pentane, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, decalin, ISOPAR (registered trademark) E or ISOPAR (registered trademark) G; ethers, such as diethyl ether, isopropyl ether, methyl tert-butyl ether, methyl tert-amyl ether, dioxane, tetrahydrofuran, 2-methyltetrahydrofuran, 1,2-dimethoxyethane or 1,2-diethoxyethane; and their mixtures.

[0381] The lithiation or magnesium complexation can be carried out in an inert atmosphere and prepared at a temperature of 0 °C to -78 °C.

[0382] The compound of formula (XVII) is known or can be prepared by known methods.

[0383] Method J2

[0384] Alternatively, the compound of formula (XVI) as defined herein can be prepared by Method J2, which comprises a metallization step of compound (XVIII) as shown in the following reaction scheme:

[0385]

[0386] Method J2

[0387] Method J2 can be carried out using a base such as n-butyllithium, lithium diisopropylamide, lithium tetramethylpiperidide, lithium bis(trimethylsilyl)amide, methyllithium or chloro-(2,2,6,6-tetramethyl-1-piperidyl)magnesium and the like, preferably under anhydrous conditions. Optionally, lithium chloride can be used in the form of a pre-formed combination with these reagents.

[0388] The solvent used in the reaction of compound (XVIII) with the base is not particularly limited as long as it forms an anhydrous reaction system without dissolving the compound to react with it or showing any specific interaction with it. Preferably, non-halogenated aliphatic, alicyclic or aromatic hydrocarbons are used, such as petroleum ether, pentane, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene, decalin, ISOPAR (registered trademark) E or ISOPAR (registered trademark) G; ethers such as diethyl ether, isopropyl ether, methyl tert-butyl ether, methyl tert-amyl ether, dioxane, tetrahydrofuran, 2-methyltetrahydrofuran, 1,2-dimethoxyethane or 1,2-diethoxyethane; and mixtures thereof.

[0389] This reaction can be carried out in an inert atmosphere and is carried out at a temperature of 0 °C to -78 °C for preparation.

[0390] Process J2 can be carried out as described in WO2006086488; WO2013170112; WO2000021928; J. Org. Chem. 2019, 84, 16, 9869-9896; Comprehensive Organic Functional Group Transformations, Volume 5, 1995, Chapter 5.02.1.2, Carbonation of Organometallic Reagents, 27-28 and the references therein.

[0391] The compound of formula (XVIII) is known or can be prepared by known methods.

[0392] Alternatively, a compound of formula (IIj) wherein A is C1-C6-alkyl can be prepared from a compound of formula (XVII) by a known method such as photocatalytic carboxylation with carbon tetrabromide and a C1-C6-alkyl alcohol as described in Journal of Organic Chemistry, 84(16), 9869-9896; 2019; or direct alkoxycarbonylation and in-situ alcoholysis by Cu-mediated trichloromethylation as described in organic Letters, 22(5), 2093-2098; 2020, or reaction with a C1-C6 alkyl chloroformate after metallation as described in MedChemComm, 9(3), 583-589; 2018.

[0393] Intermediate for preparing the compound of formula (I)

[0394] The present invention relates to intermediates for the preparation of compounds of formula (I)

[0395] Unless otherwise specified, hereinafter, R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、n, W, Y and Z have the same meanings as given above for the compounds of formula (I).

[0396] Compounds of formula (Va), (Vb) and (Vc) are provided:

[0397]

[0398] wherein

[0399] For (Va), U 2 is bromine, iodine, a mesylate group, a tosylate group or a triflate group

[0400] Provided that:

[0401] -R 1 or R 2 is not iodine

[0402] -When R 1 or R 2 is bromine, U 2 is not bromine

[0403] For (Vb), U 2 is bromine, iodine, a mesylate group, a tosylate group or a triflate group

[0404] Provided that:

[0405] -R 1 or R 3 is not iodine

[0406] - When R 1 or R 3 is bromine, U 2 is not bromine

[0407] For (Vc), U 2 is bromine, iodine, a mesylate group, a tosylate group or a triflate group

[0408] The conditions are:

[0409] - R 2 or R 3 is not iodine

[0410] - When R 2 or R 3 is bromine, U 2 is not bromine

[0411] Provide a compound of formula (VIII):

[0412]

[0413] wherein U 4 , U 5 and U 6 are independently selected from hydrogen, halogen, cyano, C1-C6-alkyl or C1-C6-haloalkyl, provided that at least one of U 4 , U 5 or U 6 is hydrogen.

[0414] Provide a compound of formula (IX):

[0415]

[0416] wherein U 7 , U 8 and U 9 are independently selected from amino, halogen, cyano, C1-C6-alkyl or C1-C6-haloalkyl, provided that at least one of U 7 , U 8 or U 9 is amino.

[0417] Compositions and formulations

[0418] The present invention also relates to a composition, in particular a composition for controlling unwanted microorganisms, which comprises one or more compounds of formula (I) or formula (II). The composition is preferably a fungicidal composition.

[0419] The composition generally comprises one or more compounds of formula (I) or formula (II) and one or more acceptable carriers, particularly one or more agriculturally acceptable carriers.

[0420] The carriers are usually inert natural or synthetic solid or liquid organic or inorganic substances. The carriers generally improve the application of the compounds, for example, on plants, plant parts or seeds. Examples of suitable solid carriers include, but are not limited to: ammonium salts, natural rock powders (such as kaolin, clay, talc, chalk, quartz, attapulgite, montmorillonite and diatomaceous earth), and synthetic rock powders (such as finely divided silica, alumina and silicates). Examples of solid carriers commonly used for preparing granules include, but are not limited to: crushed and classified natural rocks (such as calcite, marble, pumice, sepiolite and dolomite), synthetic granules of inorganic and organic powders, and granules of organic materials (such as paper, sawdust, coconut husk, corn cobs and tobacco stalks). Examples of suitable liquid carriers include, but are not limited to: water, organic solvents and combinations thereof. Examples of suitable solvents include polar and non-polar organic chemical liquids, for example from the following classes: aromatic and non-aromatic hydrocarbons (such as cyclohexane, paraffin, alkylbenzenes, xylenes, toluene alkylnaphthalenes, chlorinated aromatic hydrocarbons or chlorinated aliphatic hydrocarbons such as chlorobenzene, vinyl chloride or dichloromethane), alcohols and polyols (which may also optionally be substituted, etherified and / or esterified, such as butanol or ethylene glycol), ketones (such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone), esters (including fats and oils) and (poly)ethers, unsubstituted and substituted amines, amides (such as dimethylformamide), lactams (such as N-alkylpyrrolidone) and lactones, sulfones and sulfoxides (such as dimethyl sulfoxide). The carriers may also be liquefied gaseous diluents, i.e., liquids that are gaseous at standard temperature and standard pressure, such as aerosol propellants, such as halogenated hydrocarbons, butane, propane, nitrogen and carbon dioxide. The amount of the carrier is generally 1 to 99.99% by weight of the composition, preferably 5 to 99.9%, more preferably 10 to 99.5%, and most preferably 20 to 99%.

[0421] The composition may further comprise one or more acceptable adjuvants commonly used in formulating compositions (such as agrochemical compositions), for example one or more surfactants.

[0422] The surfactant can be an ionic (cationic or anionic) or non-ionic surfactant, such as an ionic or non-ionic emulsifier, foam former, dispersant, wetting agent, and any mixtures thereof. Examples of suitable surfactants include, but are not limited to, salts of polyacrylic acid; salts of lignosulfonic acid; salts of phenolsulfonic acid or naphthalenesulfonic acid; condensates of ethylene oxide and / or propylene oxide with fatty alcohols, fatty acids, or fatty amines (polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, such as alkylaryl polyethylene glycol ethers); substituted phenols (preferably alkylphenols or arylphenols); salts of sulfosuccinates; taurine derivatives (preferably alkyl taurates); phosphates of polyethoxylated alcohols or phenols; fatty acid esters of polyols and derivatives of compounds containing sulfate, sulfonate, or phosphate groups (e.g., alkyl sulfonates, alkyl sulfates, aryl sulfonates); and protein hydrolysates; lignosulfite waste liquor, and methylcellulose. When the compound of formula (I) or formula (II) and / or the carrier is insoluble in water and is applied with water, surfactants are usually used. Then, the amount of surfactant is generally 5% to 40% by weight of the composition.

[0423] Other examples of adjuvants commonly used in formulating agrochemical compositions include water repellents, desiccants, binders (adhesives, tackifiers, fixatives, such as carboxymethyl cellulose, natural and synthetic polymers in the form of powders, granules or latexes (such as gum arabic, polyvinyl alcohol and polyvinyl acetate), natural phospholipids (such as cephalin and lecithin) and synthetic phospholipids, polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol and methylcellulose), thickeners, stabilizers (e.g., low temperature stabilizers, preservatives, antioxidants, light stabilizers or other reagents that improve chemical and / or physical stability), dyes or pigments (such as inorganic pigments, e.g., iron oxide, titanium oxide and Prussian blue; organic dyes, e.g., alizarin, azo and metal phthalocyanine dyes), defoamers (such as silicone defoamers and magnesium stearate), preservatives (such as dichlorobenzene and benzyl alcohol hemiacetal), secondary thickeners (cellulose derivatives, acrylic derivatives, xanthan gum, modified clays and finely divided silica), tackifiers, gibberellins and processing aids, mineral oils and vegetable oils, fragrances, waxes, nutrients (including micronutrients, such as iron salts, manganese salts, boron salts, copper salts, cobalt salts, molybdenum salts and zinc salts), protective colloids, thixotropic substances, penetrants, chelating agents and complexing agents.

[0424] The selection of the adjuvant is related to the intended application mode and / or physical properties of the compound of formula (I) or formula (II). In addition, the adjuvant can be selected to impart specific properties (technical, physical and / or biological properties) to the composition or the use form prepared therefrom. The selection of the adjuvant can be such that the composition is customized for specific needs.

[0425] The composition can be in any conventional form, such as solutions (e.g., aqueous solutions), emulsions, wettable powders, water-based and oil-based suspensions, powders, dusts, pastes, soluble powders, soluble granules, broadcast granules, suspoemulsion concentrates, natural or synthetic products impregnated with one or more compounds of the invention, fertilizers, and microcapsules in polymers. The compounds of formula (I) or formula (II) can be present in suspended, emulsified or dissolved form.

[0426] The composition can be provided to the end user as a ready-to-use formulation, i.e., the composition can be applied directly to the plants or seeds by means of a suitable device such as a spraying or dusting device. Alternatively, the composition can be provided to the end user in the form of a concentrate, which must be diluted before use, preferably with water.

[0427] The composition can be prepared in a conventional manner, for example by mixing one or more compounds of formula (I) or formula (II) with one or more suitable auxiliaries (such as those disclosed above).

[0428] The composition generally contains from 0.01 to 99% by weight, from 0.05 to 98% by weight, preferably from 0.1 to 95% by weight, more preferably from 0.5 to 90% by weight, most preferably from 1 to 80% by weight of the compound of formula (I) or formula (II).

[0429] The compounds and the compositions containing them can be mixed with other active ingredients such as fungicides, bactericides, acaricides, nematicides, insecticides, herbicides, fertilizers, growth regulators, safeners or chemical pheromones. This can broaden the activity spectrum or prevent the development of resistance. Examples of known fungicides, insecticides, acaricides, nematicides and bactericides are disclosed in the "Pesticide Manual", 17th Edition.

[0430] The active ingredients shown herein by their common names are known and are described, for example, in the "Pesticide Manual" (16th Ed. British Crop Protection Council) or can be searched on the Internet (such as www.alanwood.net / pesticides).

[0431] In the case where compound (A) or compound (B) can exist in tautomeric forms, such compounds are understood hereinabove and hereinafter to also include the corresponding tautomeric forms, where applicable, even if these are not specifically mentioned in each case.

[0432] Examples of fungicides that can be mixed with the compounds of formula (I) or formula (II) and the compositions of the invention are:

[0433] 1) Ergosterol biosynthesis inhibitors, such as (1.001) cyproconazole, (1.002) difenoconazole, (1.003) epoxiconazole, (1.004) fenhexamid, (1.005) fenpropidin, (1.006) fenpropimorph, (1.007) fenpyrazamine, (1.008) fluquinconazole, (1.009) flutriafol, (1.010) imazalil, (1.011) imazalil sulfate, (1.012) ipconazole, (1.013) metconazole, (1.014) myclobutanil, (1.015) paclobutrazol, (1.016) prochloraz, (1.017) propiconazole, (1.018) prothioconazole, (1.019) pyrisoxazole, (1.020) spiroxamine, (1.021) tebuconazole, (1.022) tetraconazole, (1.023) triadimenol, (1.024) tridemorph, (1.025) triticonazole, (1.026) (1R,2S,5S)-5-(4-chlorobenzyl)-2-(chloromethyl)-2-methyl-1-(1H-1,2,4-triazol-1-ylmethyl)cyclopentanol, (1.027) (1S,2R,5R)-5-(4-chlorobenzyl)-2-(chloromethyl)-2-methyl-1-(1H-1,2,4-triazol-1-ylmethyl)cyclopentanol, (1.028) (2R)-2-(1-chlorocyclopropyl)-4-[(1R)-2,2-dichlorocyclopropyl]-1-(1H-1,2,4-triazol-1-yl)butan-2-ol, (1.029) (2R)-2-(1-chlorocyclopropyl)-4-[(1S)-2,2-dichlorocyclopropyl]-1-(1H-1,2,4-triazol-1-yl)butan-2-ol, (1.030) (2R)-2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1H-1,2,4-triazol-1-yl)propan-2-ol, (1.(1.031) (2S)-2-(1-chlorocyclopropyl)-4-[(1R)-2,2-dichlorocyclopropyl]-1-(1H-1,2,4-triazol-1-yl)butan-2-ol, (1.032) (2S)-2-(1-chlorocyclopropyl)-4-[(1S)-2,2-dichlorocyclopropyl]-1-(1H-1,2,4-triazol-1-yl)butan-2-ol, (1.033) (2S)-2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1H-1,2,4-triazol-1-yl)propan-2-ol, (1.034) (R)-[3-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)-1,2-oxazol-4-yl](pyridin-3-yl)methanol, (1.035) (S)-[3-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)-1,2-oxazol-4-yl](pyridin-3-yl)methanol, (1.036) [3-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)-1,2-oxazol-4-yl](pyridin-3-yl)methanol, (1.037) 1-({(2R,4S)-2-[2-chloro-4-(4-chlorophenoxy)phenyl]-4-methyl-1,3-dioxolan-2-yl}methyl)-1H-1,2,4-triazole, (1.038) 1-({(2S,4S)-2-[2-chloro-4-(4-chlorophenoxy)phenyl]-4-methyl-1,3-dioxolan-2-yl}methyl)-1H-1,2,4-triazole, (1.039) 1-{[3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiranyl]methyl}-1H-1,2,4-triazol-5-yl thiocyanate, (1.040) 1-{[rel(2R,3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiranyl]methyl}-1H-1,2,4-triazol-5-yl thiocyanate, (1.041) 1-{[rel(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiranyl]methyl}-1H-1,2,4-triazol-5-yl thiocyanate, (1.042) 2-[(2R,4R,5R)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylhept-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.043) 2-[(2R,4R,5S)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylhept-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.044) 2-[(2R,4S,5R)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylhept-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.045) 2-[(2R,4S,5S)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylhept-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.046) 2-[(2S,4R,5R)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylhept-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.047) 2-[(2S,4R,5S)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylhept-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.048) 2-[(2S,4S,5R)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylhept-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.049) 2-[(2S,4S,5S)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylhept-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.050) 2-[1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylhept-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.051) 2-[2-chloro-4-(2,4-dichlorophenoxy)phenyl]-1-(1H-1,2,4-triazol-1-yl)propan-2-ol, (1.052) 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-1-(1H-1,2,4-triazol-1-yl)butan-2-ol, (1.053) 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1H-1,2,4-triazol-1-yl)butan-2-ol, (1.054) 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1H-1,2,4-triazol-1-yl)pentan-2-ol, (1.055) Mefentrifluconazole, (1.056) 2-{[3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxirane-2-yl]methyl}-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.057) 2-{[rel(2R,3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxirane-2-yl]methyl}-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.058) 2-{[rel(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxirane-2-yl]methyl}-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.059) 5-(4-chlorobenzyl)-2-(chloromethyl)-2-methyl-1-(1H-1,2,4-triazol-1-ylmethyl)cyclopentanol, (1.060) 5-(allylsulfanyl)-1-{[3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxirane-2-yl]methyl}-1H-1,2,4-triazole, (1.061) 5-(allylsulfanyl)-1-{[rel(2R,3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxirane-2-yl]methyl}-1H-1,2,4-triazole, (1.062) 5-(allylsulfanyl)-1-{[rel(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxirane-2-yl]methyl}-1H-1,2,4-triazole, (1.063) N'-(2,5-dimethyl-4-{[3-(1,1,2,2-tetrafluoroethoxy)phenyl]sulfanyl}phenyl)-N-ethyl-N-methylformamidine, (1.064) N'-(2,5-dimethyl-4-{[3-(2,2,2-trifluoroethoxy)phenyl]sulfanyl}phenyl)-N-ethyl-N-methylformamidine, (1.065) N'-(2,5-dimethyl-4-{[3-(2,2,3,3-tetrafluoropropoxy)phenyl]sulfanyl}phenyl)-N-ethyl-N-methylformamidine, (1.066) N'-(2,5-dimethyl-4-{[3-(pentafluoroethoxy)phenyl]sulfanyl}phenyl)-N-ethyl-N-methylformamidine, (1.067) N'-(2,5-dimethyl-4-{3-[(1,1,2,2-tetrafluoroethyl)sulfanyl]phenoxy}phenyl)-N-ethyl-N-methylformamidine, (1.068) N'-(2,5-dimethyl-4-{3-[(2,2,2-trifluoroethyl)sulfanyl]phenoxy}phenyl)-N-ethyl-N-methylformamidine, (1.069) N'-(2,5-dimethyl-4-{3-[(2,2,3,3-tetrafluoropropyl)sulfanyl]phenoxy}phenyl)-N-ethyl-N-methylformamidine, (1.070) N'-(2,5-dimethyl-4-{3-[(pentafluoroethyl)sulfanyl]phenoxy}phenyl)-N-ethyl-N-methylformamidine, (1.071) N'-(2,5-dimethyl-4-phenoxyphenyl)-N-ethyl-N-methylformamidine, (1.072) N'-(4-{[3-(difluoromethoxy)phenyl]sulfanyl}-2,5-dimethylphenyl)-N-ethyl-N-methylformamidine, (1.073) N'-(4-{3-[(difluoromethyl)sulfanyl]phenoxy}-2,5-dimethylphenyl)-N-ethyl-N-methylformamidine, (1.074) N'-[5-bromo-6-(2,3-dihydro-1H-inden-2-yloxy)-2-methylpyridin-3-yl]-N-ethyl-N-methylformamidine, (1.N'-{4-[(4,5-dichloro-1,3-thiazol-2-yl)oxy]-2,5-dimethylphenyl}-N-ethyl-N-methylformamidine, (1.076) N'-{5-bromo-6-[(1R)-1-(3,5-difluorophenyl)ethoxy]-2-methylpyridin-3-yl}-N-ethyl-N-methylformamidine, (1.077) N'-{5-bromo-6-[(1S)-1-(3,5-difluorophenyl)ethoxy]-2-methylpyridin-3-yl}-N-ethyl-N-methylformamidine, (1.078) N'-{5-bromo-6-[(cis-4-isopropylcyclohexyl)oxy]-2-methylpyridin-3-yl}-N-ethyl-N-methylformamidine, (1.079) N'-{5-bromo-6-[(trans-4-isopropylcyclohexyl)oxy]-2-methylpyridin-3-yl}-N-ethyl-N-methylformamidine, (1.080) N'-{5-bromo-6-[1-(3,5-difluorophenyl)ethoxy]-2-methylpyridin-3-yl}-N-ethyl-N-methylformamidine, (1.081) Ipfentrifluconazole, (1.082) 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1H-1,2,4-triazol-1-yl)propan-2-ol, (1.083) 2-[6-(4-bromophenoxy)-2-(trifluoromethyl)-3-pyridinyl]-1-(1,2,4-triazol-1-yl)propan-2-ol, (1.084) 2-[6-(4-chlorophenoxy)-2-(trifluoromethyl)-3-pyridinyl]-1-(1,2,4-triazol-1-yl)propan-2-ol, (1.085) 3-[2-(1-chlorocyclopropyl)-3-(3-chloro-2-fluorophenyl)-2-hydroxypropyl]imidazole-4-carbonitrile, (1.086) 4-[[6-[rac-(2R)-2-(2,4-difluorophenyl)-1,1-difluoro-2-hydroxy-3-(5-thioxo-4H-1,2,4-triazol-1-yl)propyl]-3-pyridinyl]oxy]benzonitrile, (1.087) N-isopropyl-N'-[5-methoxy-2-methyl-4-(2,2,2-trifluoro-1-hydroxy-1-phenylethyl)phenyl]-N-methyliminocarboxamide, (1.088) N'-{5-bromo-2-methyl-6-[(1-propoxypropan-2-yl)oxy]pyridin-3-yl}-N-ethyl-N-methyliminocarboxamide.

[0434] 2) Inhibitors of respiratory chain complex I or II, such as (2.001) benzovindiflupyr, (2.002) bixafen, (2.003) boscalid, (2.004) carboxin, (2.005) fluopyram, (2.006) flutolanil, (2.007) fluxapyroxad, (2.008) furametpyr, (2.009) Isofetamid, (2.010) isopyrazam (trans-epimeric enantiomer 1R,4S,9S), (2.011) isopyrazam (trans-epimeric enantiomer 1S,4R,9R), (2.012) isopyrazam (trans-epimeric racemate 1RS,4SR,9SR), (2.013) isopyrazam (mixture of cis-epimeric racemate 1RS,4SR,9RS and trans-epimeric racemate 1RS,4SR,9SR), (2.014) isopyrazam (cis-epimeric enantiomer 1R,4S,9R), (2.015) isopyrazam (cis-epimeric enantiomer 1S,4R,9S), (2.016) isopyrazam (cis-epimeric racemate 1RS,4SR,9RS), (2.017) penflufen, (2.018) penthiopyrad, (2.019) pydiflumetofen, (2.020) pyraziflumid, (2.021) sedaxane, (2.022) 1,3-dimethyl-N-(1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl)-1H-pyrazole-4-carboxamide, (2.023) 1,3-dimethyl-N-[(3R)-1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl]-1H-pyrazole-4-carboxamide, (2.024) 1,3-dimethyl-N-[(3S)-1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl]-1H-pyrazole-4-carboxamide, (2.025) 1-methyl-3-(trifluoromethyl)-N-[2'-(trifluoromethyl)biphenyl-2-yl]-1H-pyrazole-4-carboxamide, (2.026) 2-fluoro-6-(trifluoromethyl)-N-(1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl)benzamide, (2.027) 3-(difluoromethyl)-1-methyl-N-(1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl)-1H-pyrazole-4-carboxamide, (2.(2.028) inpyrfluxam, (2.029) 3-(difluoromethyl)-1-methyl-N-[(3S)-1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl]-1H-pyrazole-4-carboxamide, (2.030) fluindapyr, (2.031) 3-(difluoromethyl)-N-[(3R)-7-fluoro-1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl]-1-methyl-1H-pyrazole-4-carboxamide, (2.032) 3-(difluoromethyl)-N-[(3S)-7-fluoro-1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl]-1-methyl-1H-pyrazole-4-carboxamide, (2.033) 5,8-difluoro-N-[2-(2-fluoro-4-{[4-(trifluoromethyl)pyridin-2-yl]oxy}phenyl)ethyl]quinazolin-4-amine, (2.034) N-(2-cyclopentyl-5-fluorobenzyl)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.035) N-(2-tert-butyl-5-methylbenzyl)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.036) N-(2-tert-butylbenzyl)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.037) N-(5-chloro-2-ethylbenzyl)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.038) isoflucypram, (2.039) N-[(1R,4S)-9-(dichloromethylene)-1,2,3,4-tetrahydro-1,4-methano-naphthalen-5-yl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.040) N-[(1S,4R)-9-(dichloromethylene)-1,2,3,4-tetrahydro-1,4-methano-naphthalen-5-yl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.041) N-[1-(2,4-dichlorophenyl)-1-methoxypropan-2-yl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.042) N-[2-chloro-6-(trifluoromethyl)benzyl]-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.043) N-[3-chloro-2-fluoro-6-(trifluoromethyl)benzyl]-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.044) N-[5-chloro-2-(trifluoromethyl)benzyl]-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.045) N-Cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-N-[5-methyl-2-(trifluoromethyl)benzyl]-1H-pyrazole-4-carboxamide, (2.046) N-Cyclopropyl-3-(difluoromethyl)-5-fluoro-N-(2-fluoro-6-isopropylbenzyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.047) N-Cyclopropyl-3-(difluoromethyl)-5-fluoro-N-(2-isopropyl-5-methylbenzyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.048) N-Cyclopropyl-3-(difluoromethyl)-5-fluoro-N-(2-isopropylbenzyl)-1-methyl-1H-pyrazole-4-thiocarboxamide, (2.049) N-Cyclopropyl-3-(difluoromethyl)-5-fluoro-N-(2-isopropylbenzyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.050) N-Cyclopropyl-3-(difluoromethyl)-5-fluoro-N-(5-fluoro-2-isopropylbenzyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.051) N-Cyclopropyl-3-(difluoromethyl)-N-(2-ethyl-4,5-dimethylbenzyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.052) N-Cyclopropyl-3-(difluoromethyl)-N-(2-ethyl-5-fluorobenzyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.053) N-Cyclopropyl-3-(difluoromethyl)-N-(2-ethyl-5-methylbenzyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.054) N-Cyclopropyl-N-(2-cyclopropyl-5-fluorobenzyl)-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.055) N-Cyclopropyl-N-(2-cyclopropyl-5-methylbenzyl)-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.056) N-Cyclopropyl-N-(2-cyclopropylbenzyl)-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.057) pyrapropoyne, (2.058) N-[rac-(1S,2S)-2-(2,4-dichlorophenyl)cyclobutyl]-2-(trifluoromethyl)nicotinamide, (2.059) N-[(1S,2S)-2-(2,4-dichlorophenyl)cyclobutyl]-2-(trifluoromethyl)nicotinamide.

[0435] 3) Inhibitors of respiratory chain complex III, such as (3.001) ametoctradin, (3.002) amisulbrom, (3.003) azoxystrobin, (3.004) coumethoxystrobin, (3.005) coumoxystrobin, (3.006) cyazofamid, (3.007) dimoxystrobin, (3.008) enoxastrobin, (3.009) famoxadone, (3.010) fenamidone, (3.011) flufenoxystrobin, (3.012) fluoxastrobin, (3.013) kresoxim-methyl, (3.014) metominostrobin, (3.015) orysastrobin, (3.016) picoxystrobin, (3.017) pyraclostrobin, (3.018) pyrametostrobin, (3.019) pyraoxystrobin, (3.020) trifloxystrobin, (3.021) (2E)-2-{2-[({[(1E)-1-(3-{[(E)-1-fluoro-2-phenylethenyl]oxy}phenyl)ethylidene]amino}oxy)methyl]phenyl}-2-(methoxyimino)-N-methylacetamide, (3.022) (2E,3Z)-5-{[1-(4-chlorophenyl)-1H-pyrazol-3-yl]oxy}-2-(methoxyimino)-N,3-dimethylpent-3-enamide, (3.023) (2R)-2-{2-[(2,5-dimethylphenoxy)methyl]phenyl}-2-methoxy-N-methylacetamide, (3.024) (2S)-2-{2-[(2,5-dimethylphenoxy)methyl]phenyl}-2-methoxy-N-methylacetamide, (3.025) fenpicoxamid, (3.026) mandestrobin, (3.027) N-(3-ethyl-3,5,5-trimethylcyclohexyl)-3-formamido-2-hydroxybenzamide, (3.028) (2E,3Z)-5-{[1-(4-chloro-2-fluorophenyl)-1H-pyrazol-3-yl]oxy}-2-(methoxyimino)-N,3-dimethylpent-3-enamide, (3.Methyl {5-[3-(2,4-dimethylphenyl)-1H-pyrazol-1-yl]-2-methylbenzyl}carbamate, (3.030) metyltetraprole, (3.031) florylpicoxamid.

[0436] 4) Mitotic and cell division inhibitors, such as (4.001) carbendazim, (4.002) diethofencarb, (4.003) ethaboxam, (4.004) fluopicolide, (4.005) pencycuron, (4.006) thiabendazole, (4.007) thiophanate-methyl, (4.008) zoxamide, (4.009) pyridachlometyl, (4.010) 3-chloro-5-(4-chlorophenyl)-4-(2,6-difluorophenyl)-6-methylpyridazine, (4.011) 3-chloro-5-(6-chloropyridin-3-yl)-6-methyl-4-(2,4,6-trifluorophenyl)pyridazine, (4.012) 4-(2-bromo-4-fluorophenyl)-N-(2,6-difluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.013) 4-(2-bromo-4-fluorophenyl)-N-(2-bromo-6-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.014) 4-(2-bromo-4-fluorophenyl)-N-(2-bromophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.015) 4-(2-bromo-4-fluorophenyl)-N-(2-chloro-6-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.016) 4-(2-bromo-4-fluorophenyl)-N-(2-chlorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.017) 4-(2-bromo-4-fluorophenyl)-N-(2-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.018) 4-(2-chloro-4-fluorophenyl)-N-(2,6-difluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.019) 4-(2-chloro-4-fluorophenyl)-N-(2-chloro-6-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.020) 4-(2-chloro-4-fluorophenyl)-N-(2-chlorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.021) 4-(2-chloro-4-fluorophenyl)-N-(2-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.022) 4-(4-chlorophenyl)-5-(2,6-difluorophenyl)-3,6-dimethylpyridazine, (4.023) N-(2-bromo-6-fluorophenyl)-4-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.024) N-(2-bromophenyl)-4-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.025) N-(4-chloro-2,6-difluorophenyl)-4-(2-chloro-4-fluorophenyl)-1,3-dimethyl-1H-pyrazol-5-amine, (4.026) fluopimomid.

[0437] 5) Compounds with multi-site activity, such as (5.001) bordeaux mixture, (5.002) captafol, (5.003) captan, (5.004) chlorothalonil, (5.005) copper hydroxide, (5.006) copper naphthenate, (5.007) copper oxide, (5.008) copper oxychloride, (5.009) copper(2+) sulfate, (5.010) dithianon, (5.011) dodine, (5.012) folpet, (5.013) mancozeb, (5.014) maneb, (5.015) metiram, (5.016) metiram zinc, (5.017) oxine-copper, (5.018) propineb, (5.019) sulfur and sulfur preparations (including calcium polysulfide), (5.020) thiram, (5.021) zineb, (5.022) ziram, (5.023) 6-ethyl-5,7-dioxo-6,7-dihydro-5H-pyrrolo[3',4':5,6][1,4]dithiino[2,3-c][1,2]thiazole-3-carbonitrile.

[0438] 6) Compounds that induce host defense, such as (6.001) acibenzolar-S-methyl, (6.002) isotianil, (6.003) probenazole, (6.004) tiadinil.

[0439] 7) Amino acid and / or protein biosynthesis inhibitors, such as (7.001) cyprodinil, (7.002) kasugamycin, (7.003) kasugamycin hydrochloride hydrate, (7.004) oxytetracycline, (7.005) pyrimethanil, (7.006) 3-(5-fluoro-3,3,4,4-tetramethyl-3,4-dihydroisoquinolin-1-yl)quinoline.

[0440] 8) ATP generation inhibitors, such as (8.001) silthiofam.

[0441] 9) Cell wall synthesis inhibitors, such as (9.001) benthiavalicarb, (9.002) dimethomorph, (9.003) flumorph, (9.004) iprovalicarb, (9.005) mandipropamid, (9.006) pyrimorph, (9.007) valifenalate, (9.008) (2E)-3-(4-tert-butylphenyl)-3-(2-chloropyridin-4-yl)-1-(morpholin-4-yl)prop-2-en-1-one, (9.009) (2Z)-3-(4-tert-butylphenyl)-3-(2-chloropyridin-4-yl)-1-(morpholin-4-yl)prop-2-en-1-one.

[0442] 10) Lipid and membrane synthesis inhibitors, such as (10.001) propamocarb, (10.002) propamocarb hydrochloride, (10.003) tolclofos-methyl.

[0443] 11) Melanin biosynthesis inhibitors, such as (11.001) tricyclazole, (11.002) tolprocarb.

[0444] 12) Nucleic acid synthesis inhibitors, such as (12.001) benalaxyl, (12.002) benalaxyl-M (kiralaxyl), (12.003) metalaxyl, (12.004) metalaxyl-M (mefenoxam).

[0445] 13) Signal transduction inhibitors, such as (13.001) fludioxonil, (13.002) iprodione, (13.003) procymidone, (13.004) proquinazid, (13.005) quinoxyfen, (13.006) vinclozolin.

[0446] 14) Compounds used as uncouplers, such as (14.001) fluazinam, (14.002) meptyldinocap.

[0447] 15) Other fungicides, which are selected from (15.001) abscisic acid, (15.002) benthiazole, (15.003) bethoxazin, (15.004) capsimycin, (15.005) carvone, (15.006) chinomethionat, (15.007) cufraneb, (15.008) cyflufenamid, (15.009) cymoxanil, (15.010) cyprosulfamide, (15.011) flutianil, (15.012) fosetyl-aluminium, (15.013) fosetyl-calcium, (15.014) fosetyl-sodium, (15.015) methyl isothiocyanate, (15.016) metrafenone, (15.017) mildiomycin, (15.018) natamycin, (15.019) nickel dimethyldithiocarbamate, (15.020) nitrothal-isopropyl, (15.021) oxamocarb, (15.022) Oxathiapiprolin, (15.023) oxyfenthiin, (15.024) pentachlorophenol and its salts, (15.025) phosphorous acid and its salts, (15.026) propamocarb-fosetylate, (15.027) pyriofenone (chlazafenone), (15.028) tebufloquin, (15.029) tecloftalam, (15.030) tolnifanide, (15.031) 1-(4-{4-[(5R)-5-(2,6-difluorophenyl)-4,5-dihydro-1,2-oxazol-3-yl]-1,3-thiazol-2-yl}piperidin-1-yl)-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]ethanone, (15.032) 1-(4-{4-[(5S)-5-(2,6-difluorophenyl)-4,5-dihydro-1,2-oxazol-3-yl]-1,3-thiazol-2-yl}piperidin-1-yl)-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]ethanone, (15.033) 2-(6-benzylpyridin-2-yl)quinazoline, (15.034) dipymetitrone, (15.035) 2-[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]-1-[4-(4-{5-[2-(prop-2-yn-1-yloxy)phenyl]-4,5-dihydro-1,2-oxazol-3-yl}-1,3-thiazol-2-yl)piperidin-1-yl]ethanone, (15.036) 2-[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]-1-[4-(4-{5-[2-chloro-6-(prop-2-yn-1-yloxy)phenyl]-4,5-dihydro-1,2-oxazol-3-yl}-1,3-thiazol-2-yl)piperidin-1-yl]ethanone, (15.037) 2-[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]-1-[4-(4-{5-[2-fluoro-6-(prop-2-yn-1-yloxy)phenyl]-4,5-dihydro-1,2-oxazol-3-yl}-1,3-thiazol-2-yl)piperidin-1-yl]ethanone, (15.038) 2-[6-(3-fluoro-4-methoxyphenyl)-5-methylpyridin-2-yl]quinazoline, (15.039) 2-{(5R)-3-[2-(1-{[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazol-4-yl]-4,5-dihydro-1,2-oxazol-5-yl}-3-chlorophenyl methanesulfonate, (15.040) 2-{(5S)-3-[2-(1-{[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazol-4-yl]-4,5-dihydro-1,2-oxazol-5-yl}-3-chlorophenyl methanesulfonate, (15.041) Ipflufenoquin, (15.042) 2-{2-fluoro-6-[(8-fluoro-2-methylquinolin-3-yl)oxy]phenyl}propan-2-ol, (15.043) fluoxapiprolin, (15.044) 2-{3-[2-(1-{[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazol-4-yl]-4,5-dihydro-1,2-oxazol-5-yl}phenyl methanesulfonate, (15.045) 2-phenylphenol and salts, (15.046) 3-(4,4,5-trifluoro-3,3-dimethyl-3,4-dihydroisoquinolin-1-yl)quinoline, (15.047) quinofumelin, (15.048) 4-Amino-5-fluoropyrimidin-2-ol (tautomeric form: 4-amino-5-fluoropyrimidin-2(1H)-one), (15.049) 4-oxo-4-[(2-phenylethyl)amino]butanoic acid, (15.050) 5-amino-1,3,4-thiadiazole-2-thiol, (15.051) 5-chloro-N'-phenyl-N'-(prop-2-yn-1-yl)thiophene-2-sulfonylhydrazide, (15.052) 5-fluoro-2-[(4-fluorobenzyl)oxy]pyrimidin-4-amine, (15.053) 5-fluoro-2-[(4-methylbenzyl)oxy]pyrimidin-4-amine, (15.054) 9-fluoro-2,2-dimethyl-5-(quinolin-3-yl)-2,3-dihydro-1,4-benzoxazepine, (15.055) {6-[({[(Z)-(1-methyl-1H-tetrazol-5-yl)(phenyl)methylene]amino}oxy)methyl]pyridin-2-yl}but-3-yn-1-yl carbamate, (15.056) (2Z)-ethyl 3-amino-2-cyano-3-phenylacrylate, (15.057) phenazine-1-carboxylic acid, (15.058) propyl 3,4,5-trihydroxybenzoate, (15.059) quinolin-8-ol, (15.060) quinolin-8-ol sulfate (2:1), (15.061) tert-butyl {6-[({[(1-methyl-1H-tetrazol-5-yl)(phenyl)methylene]amino}oxy)methyl]pyridin-2-yl}carbamate, (15.062) 5-fluoro-4-imino-3-methyl-1-[(4-methylphenyl)sulfonyl]-3,4-dihydropyrimidin-2(1H)-one, (15.063) aminopyrifen, (15.064) (N'-[2-chloro-4-(2-fluorophenoxy)-5-methylphenyl]-N-ethyl-N-methylformimidamide), (15.065) (N'-(2-chloro-5-methyl-4-phenoxyphenyl)-N-ethyl-N-methylformimidamide), (15.066) (2-{2-[(7,8-difluoro-2-methylquinolin-3-yl)oxy]-6-fluorophenyl}propan-2-ol), (15.067) (5-bromo-1-(5,6-dimethylpyridin-3-yl)-3,3-dimethyl-3,4-dihydroisoquinoline), (15.068) (3-(4,4-difluoro-5,5-dimethyl-4,5-dihydrothieno[2,3-c]pyridin-7-yl)quinoline), (15.069) (1-(4,5-dimethyl-1H-benzimidazol-1-yl)-4,4-difluoro-3,3-dimethyl-3,4-dihydroisoquinoline), (15.070) 8-fluoro-3-(5-fluoro-3,3-dimethyl-3,4-dihydroisoquinolin-1-yl)quinolone, (15.071) 8-fluoro-3-(5-fluoro-3,3,4,4-tetramethyl-3,4-dihydroisoquinolin-1-yl)quinolone, (15.072) 3-(4,4-difluoro-3,3-dimethyl-3,4-dihydroisoquinolin-1-yl)-8-fluoroquinoline, (15.073) (N-methyl-N-phenyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide), (15.074) methyl 4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenylcarbamate, (15.075) (N-{4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl}cyclopropanecarboxamide), (15.076) N-methyl-4-(5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl)-benzamide, (15.077) N-[(E)-methoxyiminomethyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, (15.078) N-[(Z)-methoxyiminomethyl]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, (15.079) N-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]cyclopropanecarboxamide, (15.080) N-(2-fluorophenyl)-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, (15.081) 2,2-difluoro-N-methyl-2-[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]acetamide, (15.082) N-allyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl)phenyl]methyl]acetamide, (15.083) N-[(E)-N-methoxy-C-methyl-carbodiimido]-4-(5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, (15.084) N-[(Z)-N-methoxy-C-methyl-carbodiimido]-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, (15.085) N-allyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-propanamide, (15.086) 4,4-dimethyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-pyrrolidin-2-one, (15.087) N-methyl-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]-thiobenzamide, (15.088) 5-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]pyrrolidin-2-one, (15.089) N-((2,3-difluoro-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-3,3,3-trifluoro-propanamide, (15.090) 1-Methoxy-1-methyl-3-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, (15.091) 1,1-Diethyl-3-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, (15.092) N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide, (15.093) N-Methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]cyclopropanecarboxamide, (15.094) 1-Methoxy-3-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, (15.095) N-Methoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl)cyclopropanecarboxamide, (15.096) N,2-Dimethoxy-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]propanamide, (15.097) N-Ethyl-2-methyl-N-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl)phenyl]methyl]propanamide, (15.098) 1-Methoxy-3-methyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, (15.099) 1,3-Dimethoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, (15.100) 3-Ethyl-1-methoxy-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]urea, (15.101) 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]piperidin-2-one, (15.102) 4,4-Dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one, (15.103) 5,5-Dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one, (15.104) 3,3-Dimethyl-1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]piperidin-2-one, (15.105) 1-[[3-Fluoro-4-(5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]azepan-2-one, (15.106) 4,4-Dimethyl-2-[[4-(5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one, (15.(107) 5,5-Dimethyl-2-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]isoxazolidin-3-one, (15.108) Ethyl 1-{4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzyl}-1H-pyrazole-4-carboxylate, (15.109) N,N-Dimethyl-1-{4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzyl}-1H-1,2,4-triazol-3-amine, (15.110) N-{2,3-Difluoro-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzyl}butanamide, (15.111) N-(1-Methylcyclopropyl)-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, (15.112) N-(2,4-Difluorophenyl)-4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]benzamide, (15.113) 1-(5,6-Dimethylpyridin-3-yl)-4,4-difluoro-3,3-dimethyl-3,4-dihydroisoquinoline, (15.114) 1-(6-(Difluoromethyl)-5-methylpyridin-3-yl)-4,4-difluoro-3,3-dimethyl-3,4-dihydroisoquinoline, (15.115) 1-(5-(Fluoromethyl)-6-methylpyridin-3-yl)-4,4-difluoro-3,3-dimethyl-3,4-dihydroisoquinoline, (15.116) 1-(6-(Difluoromethyl)-5-methoxypyridin-3-yl)-4,4-difluoro-3,3-dimethyl-3,4-dihydroisoquinoline, (15.117) 4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl dimethylcarbamate, (15.118) N-{4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl}propanamide, (15.119) 3-[2-(1-{[5-Methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazol-4-yl]-1,5-dihydro-2,4-benzodioxepin-6-yl methanesulfonate, (15.120) 9-Fluoro-3-[2-(1-{[5-Methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazol-4-yl]-1,5-dihydro-2,4-benzodioxepin-6-yl methanesulfonate, (15.121) 3-[2-(1-{[3,5-Bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazol-4-yl]-1,5-dihydro-2,4-benzodioxepin-6-yl methanesulfonate, (15.122) 3-[2-(1-{[3,5-Bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl}piperidin-4-yl)-1,3-thiazol-4-yl]-9-fluoro-1,5-dihydro-2,4-benzodioxepin-6-yl methanesulfonate, (15.123) 1-(6,7-dimethylpyrazolo[1,5-a]pyridin-3-yl)-4,4-difluoro-3,3-dimethyl-3,4-dihydroisoquinoline, (15.124) 8-fluoro-N-(4,4,4-trifluoro-2-methyl-1-phenylbutan-2-yl)quinoline-3-carboxamide, (15.125) 8-fluoro-N-[(2S)-4,4,4-trifluoro-2-methyl-1-phenylbutan-2-yl]quinoline-3-carboxamide, (15.126) N-(2,4-dimethyl-1-phenylpentan-2-yl)-8-fluoroquinoline-3-carboxamide and (15.127) N-[(2S)-2,4-dimethyl-1-phenylpentan-2-yl]-8-fluoroquinoline-3-carboxamide.

[0448] All named admixtures of classes (1) to (15) may optionally (if their functional groups permit) form salts with suitable bases or acids

[0449] Another aspect of the invention relates to one or more of the following compound combinations:

[0450] (I.0001)+(1.001), (I.0001)+(1.002), (I.0001)+(1.003), (I.0001)+(1.004), (I.0001)+(1.005), (I.0001)+(1.006), (I.0001)+(1.007), (I.0001)+(1.008), (I.0001)+(1.009), (I.0001)+(1.010), (I.0001)+(1.011), (I.0001)+(1.012), (I.0001)+(1.013), (I.0001)+(1.014), (I.0001)+(1.015), (I.0001)+(1.016), (I.0001)+(1.017), (I.0001)+(1.018), (I.0001)+(1.019), (I.0001)+(1.020), (I.0001)+(1.021), (I.0001)+(1.022), (I.0001)+(1.023), (I.0001)+(1.024), (I.0001)+(1.025), (I.0001)+(1.026), (I.0001)+(1.027), (I.0001)+(1.028), (I.0001)+(1.029), (I.0001)+(1.030), (I.0001)+(1.031), (I.0001)+(1.032), (I.0001)+(1.033), (I.0001)+(1.034), (I.0001)+(1.035), (I.0001)+(1.036), (I.0001)+(1.037), (I.0001)+(1.038), (I.0001)+(1.039), (I.0001)+(1.040), (I.0001)+(1.041), (I.0001)+(1.042), (I.0001)+(1.043), (I.0001)+(1.044), (I.0001)+(1.045), (I.0001)+(1.046), (I.0001)+(1.047), (I.0001)+(1.048), (I.0001)+(1.049), (I.0001)+(1.050), (I.0001)+(1.051), (I.0001)+(1.052), (I.0001)+(1.053), (I.0001)+(1.054), (I.0001)+(1.055), (I.0001)+(1.056), (I.0001)+(1.057), (I.0001)+(1.058), (I.0001)+(1.059), (I.0001) + (1.060), (I.0001) + (1.061), (I.0001) + (1.062), (I.0001) + (1.063), (I.0001) + (1.064), (I.0001) + (1.065), (I.0001) + (1.066), (I.0001) + (1.067), (I.0001) + (1.068), (I.0001) + (1.069), (I.0001) + (1.070), (I.0001) + (1.071), (I.0001) + (1.072), (I.0001) + (1.073), (I.0001) + (1.074), (I.0001) + (1.075), (I.0001) + (1.076), (I.0001) + (1.077), (I.0001) + (1.078), (I.0001) + (1.079), (I.0001) + (1.080), (I.0001) + (1.081), (I.0001) + (1.082), (I.0001) + (1.083), (I.0001) + (1.084), (I.0001) + (1.085), (I.0001) + (1.086), (I.0001) + (1.087), (I.0001) + (1.088), (I.0001) + (1.089), (I.0001) + (1.090), (I.0001) + (1.091), (I.0001) + (2.001), (I.0001) + (2.002), (I.0001) + (2.003), (I.0001) + (2.004), (I.0001) + (2.005), (I.0001) + (2.006), (I.0001) + (2.007), (I.0001) + (2.008), (I.0001) + (2.009), (I.0001) + (2.010), (I.0001) + (2.011), (I.0001) + (2.012), (I.0001) + (2.013), (I.0001) + (2.014), (I.0001) + (2.015), (I.0001) + (2.016), (I.0001) + (2.017), (I.0001) + (2.018), (I.0001) + (2.019), (I.0001) + (2.020), (I.0001) + (2.021), (I.0001) + (2.022), (I.0001) + (2.023), (I.0001) + (2.024), (I.0001) + (2.025), (I.0001) + (2.026), (I.(I.0001)+(2.027), (I.0001)+(2.028), (I.0001)+(2.029), (I.0001)+(2.030), (I.0001)+(2.031), (I.0001)+(2.032), (I.0001)+(2.033), (I.0001)+(2.034), (I.0001)+(2.035), (I.0001)+(2.036), (I.0001)+(2.037), (I.0001)+(2.038), (I.0001)+(2.039), (I.0001)+(2.040), (I.0001)+(2.041), (I.0001)+(2.042), (I.0001)+(2.043), (I.0001)+(2.044), (I.0001)+(2.045), (I.0001)+(2.046), (I.0001)+(2.047), (I.0001)+(2.048), (I.0001)+(2.049), (I.0001)+(2.050), (I.0001)+(2.051), (I.0001)+(2.052), (I.0001)+(2.053), (I.0001)+(2.054), (I.0001)+(2.055), (I.0001)+(2.056), (I.0001)+(2.057), (I.0001)+(2.058), (I.0001)+(2.059), (I.0001)+(3.001), (I.0001)+(3.002), (I.0001)+(3.003), (I.0001)+(3.004), (I.0001)+(3.005), (I.0001)+(3.006), (I.0001)+(3.007), (I.0001)+(3.008), (I.0001)+(3.009), (I.0001)+(3.010), (I.0001)+(3.011), (I.0001)+(3.012), (I.0001)+(3.013), (I.0001)+(3.014), (I.0001)+(3.015), (I.0001)+(3.016), (I.0001)+(3.017), (I.0001)+(3.018), (I.0001)+(3.019), (I.0001)+(3.020), (I.0001)+(3.021), (I.0001)+(3.022), (I.0001)+(3.023), (I.0001)+(3.024), (I.0001)+(3.025), (I.0001)+(3.(I.0001)+(3.027), (I.0001)+(3.028), (I.0001)+(3.029), (I.0001)+(3.030), (I.0001)+(3.031), (I.0001)+(4.001), (I.0001)+(4.002), (I.0001)+(4.003), (I.0001)+(4.004), (I.0001)+(4.005), (I.0001)+(4.006), (I.0001)+(4.007), (I.0001)+(4.008), (I.0001)+(4.009), (I.0001)+(4.010), (I.0001)+(4.011), (I.0001)+(4.012), (I.0001)+(4.013), (I.0001)+(4.014), (I.0001)+(4.015), (I.0001)+(4.016), (I.0001)+(4.017), (I.0001)+(4.018), (I.0001)+(4.019), (I.0001)+(4.020), (I.0001)+(4.021), (I.0001)+(4.022), (I.0001)+(4.023), (I.0001)+(4.024), (I.0001)+(4.025), (I.0001)+(4.026), (I.0001)+(5.001), (I.0001)+(5.002), (I.0001)+(5.003), (I.0001)+(5.004), (I.0001)+(5.005), (I.0001)+(5.006), (I.0001)+(5.007), (I.0001)+(5.008), (I.0001)+(5.009), (I.0001)+(5.010), (I.0001)+(5.011), (I.0001)+(5.012), (I.0001)+(5.013), (I.0001)+(5.014), (I.0001)+(5.015), (I.0001)+(5.016), (I.0001)+(5.017), (I.0001)+(5.018), (I.0001)+(5.019), (I.0001)+(5.020), (I.0001)+(5.021), (I.0001)+(5.022), (I.0001)+(5.023), (I.0001)+(6.001), (I.0001)+(6.002), (I.0001)+(6.003), (I.0001)+(6.004), (I.(I.0001)+(7.001), (I.0001)+(7.002), (I.0001)+(7.003), (I.0001)+(7.004), (I.0001)+(7.005), (I.0001)+(7.006), (I.0001)+(8.001), (I.0001)+(9.001), (I.0001)+(9.002), (I.0001)+(9.003), (I.0001)+(9.004), (I.0001)+(9.005), (I.0001)+(9.006), (I.0001)+(9.007), (I.0001)+(9.008), (I.0001)+(9.009), (I.0001)+(10.001), (I.0001)+(10.002), (I.0001)+(10.003), (I.0001)+(11.001), (I.0001)+(11.002), (I.0001)+(12.001), (I.0001)+(12.002), (I.0001)+(12.003), (I.0001)+(12.004), (I.0001)+(13.001), (I.0001)+(13.002), (I.0001)+(13.003), (I.0001)+(13.004), (I.0001)+(13.005), (I.0001)+(13.006), (I.0001)+(14.001), (I.0001)+(14.002), (I.0001)+(15.001), (I.0001)+(15.002), (I.0001)+(15.003), (I.0001)+(15.004), (I.0001)+(15.005), (I.0001)+(15.006), (I.0001)+(15.007), (I.0001)+(15.008), (I.0001)+(15.009), (I.0001)+(15.010), (I.0001)+(15.011), (I.0001)+(15.012), (I.0001)+(15.013), (I.0001)+(15.014), (I.0001)+(15.015), (I.0001)+(15.016), (I.0001)+(15.017), (I.0001)+(15.018), (I.0001)+(15.019), (I.0001)+(15.020), (I.0001)+(15.021), (I.0001)+(15.022), (I.0001)+(15.023), (I.(I.0001)+(15.024), (I.0001)+(15.025), (I.0001)+(15.026), (I.0001)+(15.027), (I.0001)+(15.028), (I.0001)+(15.029), (I.0001)+(15.030), (I.0001)+(15.031), (I.0001)+(15.032), (I.0001)+(15.033), (I.0001)+(15.034), (I.0001)+(15.035), (I.0001)+(15.036), (I.0001)+(15.037), (I.0001)+(15.038), (I.0001)+(15.039), (I.0001)+(15.040), (I.0001)+(15.041), (I.0001)+(15.042), (I.0001)+(15.043), (I.0001)+(15.044), (I.0001)+(15.045), (I.0001)+(15.046), (I.0001)+(15.047), (I.0001)+(15.048), (I.0001)+(15.049), (I.0001)+(15.050), (I.0001)+(15.051), (I.0001)+(15.052), (I.0001)+(15.053), (I.0001)+(15.054), (I.0001)+(15.055), (I.0001)+(15.056), (I.0001)+(15.057), (I.0001)+(15.058), (I.0001)+(15.059), (I.0001)+(15.060), (I.0001)+(15.061), (I.0001)+(15.062), (I.0001)+(15.063), (I.0001)+(15.064), (I.0001)+(15.065), (I.0001)+(15.066), (I.0001)+(15.067), (I.0001)+(15.068), (I.0001)+(15.069), (I.0001)+(15.070), (I.0001)+(15.071), (I.0001)+(15.072), (I.0001)+(15.073), (I.0001)+(15.074), (I.0001)+(15.075), (I.0001)+(15.076), (I.0001), (I.0001)+(15.077), (I.0001)+(15.078), (I.(I.0001)+(15.079), (I.0001)+(15.080), (I.0001)+(15.081), (I.0001)+(15.082), (I.0001)+(15.083), (I.0001)+(15.084), (I.0001)+(15.085), (I.0001)+(15.086), (I.0001)+(15.087), (I.0001)+(15.088), (I.0001)+(15.089), (I.0001)+(15.090), (I.0001)+(15.091), (I.0001)+(15.092), (I.0001)+(15.093), (I.0001)+(15.094), (I.0001)+(15.095), (I.0001)+(15.096), (I.0001)+(15.097), (I.0001)+(15.098), (I.0001)+(15.099), (I.0001)+(15.100), (I.0001)+(15.101), (I.0001)+(15.102), (I.0001)+(15.103), (I.0001)+(15.104), (I.0001)+(15.105), (I.0001)+(15.106), (I.0001)+(15.107), (I.0001)+(15.108), (I.0001)+(15.109), (I.0001)+(15.110), (I.0001)+(15.111), (I.0001)+(15.112), (I.0001)+(15.113), (I.0001)+(15.114), (I.0001)+(15.115), (I.0001)+(15.116), (I.0001)+(15.117), (I.0001)+(15.118), (I.0001)+(15.119), (I.0001)+(15.120), (I.0001)+(15.121), (I.0001)+(15.122), (I.0001)+(15.123), (I.0001)+(15.124), (I.0001)+(15.125), (I.0001)+(15.126), (I.0001)+(15.127).

[0451] In these combinations, the first component is a compound of formula (I) as defined in Tables I.1 and I.2 (e.g., I.0001), and the second component is a fungicide selected from Groups 1 to 15 as defined herein. For example, the combination (I.0001)+(1.001) corresponds to a combination comprising compound I.0001 and cyproconazole (1.001) from Tables I.1 and I.2.

[0452] In some other embodiments, the compound combination corresponds to the above combination, wherein compound (I.0001) is replaced by any of the compounds mentioned in Tables I.1 and I.2.

[0453] The compound of formula (I) and the fungicide selected from Groups (1) to (15) can be present in a weight ratio of 100:1 to 1:100 (compound of formula (I): fungicide selected from Groups (1) to (15)), or 50:1 to 1:50, or 20:1 to 1:20. Other examples of weight ratio ranges include 95:1 to 1:95, 90:1 to 1:90, 85:1 to 1:85, 80:1 to 1:80, 75:1 to 1:75, 70:1 to 1:70, 65:1 to 1:65, 60:1 to 1:60, 55:1 to 1:55, 45:1 to 1:45, 40:1 to 1:40, 35:1 to 1:35, 30:1 to 1:30, 25:1 to 1:25, 15:1 to 1:15, 10:1 to 1:10, 5:1 to 1:5, 4:1 to 1:4, 3:1 to 1:3, 2:1 to 1:2.

[0454] Another fungicide selected from Groups 1 to 15 as defined herein can be added to the compound combination.

[0455] Another aspect of the present invention relates to one or more of the following compound combinations:

[0456] (II.001)+(1.001), (II.001)+(1.002), (II.001)+(1.003), (II.001)+(1.004), (II.001)+(1.005), (II.001)+(1.006), (II.001)+(1.007), (II.001)+(1.008), (II.001)+(1.009), (II.001)+(1.010), (II.001)+(1.011), (II.001)+(1.012), (II.001)+(1.013), (II.001)+(1.014), (II.001)+(1.015), (II.001)+(1.016), (II.001)+(1.017), (II.001)+(1.018), (II.001)+(1.019), (II.001)+(1.020), (II.001)+(1.021), (II.001)+(1.022), (II.001)+(1.023), (II.001)+(1.024), (II.001)+(1.025), (II.001)+(1.026), (II.001)+(1.027), (II.001)+(1.028), (II.001)+(1.029), (II.001)+(1.030), (II.001)+(1.031), (II.001)+(1.032), (II.001)+(1.033), (II.001)+(1.034), (II.001)+(1.035), (II.001)+(1.036), (II.001)+(1.037), (II.001)+(1.038), (II.001)+(1.039), (II.001)+(1.040), (II.001)+(1.041), (II.001)+(1.042), (II.001)+(1.043), (II.001)+(1.044), (II.001)+(1.045), (II.001)+(1.046), (II.001)+(1.047), (II.001)+(1.048), (II.001)+(1.049), (II.001)+(1.050), (II.001)+(1.051), (II.001)+(1.052), (II.001)+(1.053), (II.001)+(1.054), (II.001)+(1.055), (II.001)+(1.056), (II.001)+(1.057), (II.001)+(1.058), (II.001)+(1.059), (II.001) + (1.060), (II.001) + (1.061), (II.001) + (1.062), (II.001) + (1.063), (II.001) + (1.064), (II.001) + (1.065), (II.001) + (1.066), (II.001) + (1.067), (II.001) + (1.068), (II.001) + (1.069), (II.001) + (1.070), (II.001) + (1.071), (II.001) + (1.072), (II.001) + (1.073), (II.001) + (1.074), (II.001) + (1.075), (II.001) + (1.076), (II.001) + (1.077), (II.001) + (1.078), (II.001) + (1.079), (II.001) + (1.080), (II.001) + (1.081), (II.001) + (1.082), (II.001) + (1.083), (II.001) + (1.084), (II.001) + (1.085), (II.001) + (1.086), (II.001) + (1.087), (II.001) + (1.088), (II.001) + (1.089), (II.001) + (1.090), (II.001) + (1.091), (II.001) + (2.001), (II.001) + (2.002), (II.001) + (2.003), (II.001) + (2.004), (II.001) + (2.005), (II.001) + (2.006), (II.001) + (2.007), (II.001) + (2.008), (II.001) + (2.009), (II.001) + (2.010), (II.001) + (2.011), (II.001) + (2.012), (II.001) + (2.013), (II.001) + (2.014), (II.001) + (2.015), (II.001) + (2.016), (II.001) + (2.017), (II.001) + (2.018), (II.001) + (2.019), (I.001) + (2.020), (I.001) + (2.021), (I.001) + (2.022), (I.001) + (2.023), (I.001) + (2.024), (I.001) + (2.025), (I.001) + (2.026), (II.001) + (2.(II.001)+(2.027), (II.001)+(2.028), (II.001)+(2.029), (II.001)+(2.030), (II.001)+(2.031), (II.001)+(2.032), (II.001)+(2.033), (II.001)+(2.034), (II.001)+(2.035), (II.001)+(2.036), (II.001)+(2.037), (II.001)+(2.038), (II.001)+(2.039), (II.001)+(2.040), (II.001)+(2.041), (II.001)+(2.042), (II.001)+(2.043), (II.001)+(2.044), (II.001)+(2.045), (II.001)+(2.046), (II.001)+(2.047), (II.001)+(2.048), (II.001)+(2.049), (II.001)+(2.050), (II.001)+(2.051), (II.001)+(2.052), (II.001)+(2.053), (II.001)+(2.054), (II.001)+(2.055), (II.001)+(2.056), (II.001)+(2.057), (II.001)+(2.058), (II.001)+(2.059), (II.001)+(3.001), (II.001)+(3.002), (II.001)+(3.003), (II.001)+(3.004), (II.001)+(3.005), (II.001)+(3.006), (II.001)+(3.007), (II.001)+(3.008), (II.001)+(3.009), (II.001)+(3.010), (II.001)+(3.011), (II.001)+(3.012), (II.001)+(3.013), (II.001)+(3.014), (II.001)+(3.015), (II.001)+(3.016), (II.001)+(3.017), (II.001)+(3.018), (II.001)+(3.019), (II.001)+(3.020), (II.001)+(3.021), (II.001)+(3.022), (II.001)+(3.023), (II.001)+(3.024), (II.001)+(3.025), (II.001)+(3.026), (II.(II.001)+(3.027), (II.001)+(3.028), (II.001)+(3.029), (II.001)+(3.030), (II.001)+(3.031), (II.001)+(4.001), (II.001)+(4.002), (II.001)+(4.003), (II.001)+(4.004), (II.001)+(4.005), (II.001)+(4.006), (II.001)+(4.007), (II.001)+(4.008), (II.001)+(4.009), (II.001)+(4.010), (II.001)+(4.011), (II.001)+(4.012), (II.001)+(4.013), (II.001)+(4.014), (II.001)+(4.015), (II.001)+(4.016), (II.001)+(4.017), (II.001)+(4.018), (II.001)+(4.019), (II.001)+(4.020), (II.001)+(4.021), (II.001)+(4.022), (II.001)+(4.023), (II.001)+(4.024), (II.001)+(4.025), (II.001)+(4.026), (II.001)+(5.001), (II.001)+(5.002), (II.001)+(5.003), (II.001)+(5.004), (II.001)+(5.005), (II.001)+(5.006), (II.001)+(5.007), (II.001)+(5.008), (II.001)+(5.009), (II.001)+(5.010), (II.001)+(5.011), (II.001)+(5.012), (II.001)+(5.013), (II.001)+(5.014), (II.001)+(5.015), (II.001)+(5.016), (II.001)+(5.017), (II.001)+(5.018), (II.001)+(5.019), (II.001)+(5.020), (II.001)+(5.021), (II.001)+(5.022), (II.001)+(5.023), (II.001)+(6.001), (II.001)+(6.002), (II.001)+(6.003), (II.001)+(6.004), (II.001)+(7.001), (II.001)+(7.002), (II.001)+(7.003), (II.001)+(7.004), (II.001)+(7.005), (II.001)+(7.006), (II.001)+(8.001), (II.001)+(9.001), (II.001)+(9.002), (II.001)+(9.003), (II.001)+(9.004), (II.001)+(9.005), (II.001)+(9.006), (II.001)+(9.007), (II.001)+(9.008), (II.001)+(9.009), (II.001)+(10.001), (II.001)+(10.002), (II.001)+(10.003), (II.001)+(11.001), (II.001)+(11.002), (II.001)+(12.001), (II.001)+(12.002), (II.001)+(12.003), (II.001)+(12.004), (II.001)+(13.001), (II.001)+(13.002), (II.001)+(13.003), (II.001)+(13.004), (II.001)+(13.005), (II.001)+(13.006), (II.001)+(14.001), (II.001)+(14.002), (II.001)+(15.001), (II.001)+(15.002), (II.001)+(15.003), (II.001)+(15.004), (II.001)+(15.005), (II.001)+(15.006), (II.001)+(15.007), (II.001)+(15.008), (II.001)+(15.009), (II.001)+(15.010), (II.001)+(15.011), (II.001)+(15.012), (II.001)+(15.013), (II.001)+(15.014), (II.001)+(15.015), (II.001)+(15.016), (II.001)+(15.017), (II.001)+(15.018), (II.001)+(15.019), (II.001)+(15.020), (II.001)+(15.021), (II.001)+(15.022), (II.001)+(15.023), (II.001)+(15.(II.001)+(15.025), (II.001)+(15.026), (II.001)+(15.027), (II.001)+(15.028), (II.001)+(15.029), (II.001)+(15.030), (II.001)+(15.031), (II.001)+(15.032), (II.001)+(15.033), (II.001)+(15.034), (II.001)+(15.035), (II.001)+(15.036), (II.001)+(15.037), (II.001)+(15.038), (II.001)+(15.039), (II.001)+(15.040), (II.001)+(15.041), (II.001)+(15.042), (II.001)+(15.043), (II.001)+(15.044), (II.001)+(15.045), (II.001)+(15.046), (II.001)+(15.047), (II.001)+(15.048), (II.001)+(15.049), (II.001)+(15.050), (II.001)+(15.051), (II.001)+(15.052), (II.001)+(15.053), (II.001)+(15.054), (II.001)+(15.055), (II.001)+(15.056), (II.001)+(15.057), (II.001)+(15.058), (II.001)+(15.059), (II.001)+(15.060), (II.001)+(15.061), (II.001)+(15.062), (II.001)+(15.063), (II.001)+(15.064), (II.001)+(15.065), (II.001)+(15.066), (II.001)+(15.067), (II.001)+(15.068), (II.001)+(15.069), (II.001)+(15.070), (II.001)+(15.071), (II.001)+(15.072), (II.001)+(15.073), (II.001)+(15.074), (II.001)+(15.075), (II.001)+(15.076), (II.001), (II.001)+(15.077), (II.001)+(15.078), (II.001)+(15.(II.001)+(15.080), (II.001)+(15.081), (I.001)+(15.082), (I.001)+(15.083), (I.001)+(15.084), (I.001)+(15.085), (I.001)+(15.086), (I.001)+(15.087), (I.001)+(15.088), (I.001)+(15.089), (I.001)+(15.090), (I.001)+(15.091), (I.001)+(15.092), (I.001)+(15.093), (II.001)+(15.094), (II.001)+(15.095), (II.001)+(15.096), (II.001)+(15.097), (II.001)+(15.098), (II.001)+(15.099), (II.001)+(15.100), (II.001)+(15.101), (II.001)+(15.102), (II.001)+(15.103), (II.001)+(15.104), (II.001)+(15.105), (II.001)+(15.106), (II.001)+(15.107), (II.001)+(15.108), (II.001)+(15.109), (II.001)+(15.110), (II.001)+(15.111), (II.001)+(15.112), (II.001)+(15.113), (II.001)+(15.114), (II.001)+(15.115), (II.001)+(15.116), (II.001)+(15.117), (II.001)+(15.118), (II.001)+(15.119), (II.001)+(15.120), (II.001)+(15.121), (II.001)+(15.122), (II.001)+(15.123), (II.001)+(15.124), (II.001)+(15.125), (II.001)+(15.126), (II.001)+(15.127).

[0457] Among these conjugates, the first component is a compound of formula (II) as defined in Table II.1 (e.g., II.001), and the second component is a fungicide selected from Groups 1 to 15 as defined herein. For example, the conjugate (II.001)+(1.001) corresponds to a conjugate comprising compound II.001 from Table II.1 and cyproconazole (1.001).

[0458] In some other embodiments, the compound conjugate corresponds to the above conjugate, wherein the compound (II.001) is replaced by any of the compounds mentioned in Table II.1.

[0459] The compound of formula (II) and the fungicide selected from Groups (1) to (15) can be present in a weight ratio of 100:1 to 1:100 (compound of formula (II): fungicide selected from Groups (1) to (15)), or 50:1 to 1:50, or 20:1 to 1:20. Other examples of weight ratio ranges include 95:1 to 1:95, 90:1 to 1:90, 85:1 to 1:85, 80:1 to 1:80, 75:1 to 1:75, 70:1 to 1:70, 65:1 to 1:65, 60:1 to 1:60, 55:1 to 1:55, 45:1 to 1:45, 40:1 to 1:40, 35:1 to 1:35, 30:1 to 1:30, 25:1 to 1:25, 15:1 to 1:15, 10:1 to 1:10, 5:1 to 1:5, 4:1 to 1:4, 3:1 to 1:3, 2:1 to 1:2.

[0460] Another fungicide selected from Groups 1 to 15 as defined herein can be added to the compound conjugate.

[0461] The compound of formula (I) or (II) and the composition containing it can be combined with one or more biocontrol agents.

[0462] Examples of biocontrol agents that can be combined with the compound of formula (I) or (II) and the composition containing it are:

[0463] (A) Antimicrobial agents selected from:

[0464] (A1) Bacteria, such as (A1.1) Bacillus subtilis, in particular strain QST713 / AQ713 (available from Bayer CropScience LP, US under the name SERENADE OPTI or SERENADE ASO, accession number NRRL B21661 and described in US Patent No. 6,060,051); (A1.2) Bacillus amyloliquefaciens, in particular strain D747 (available from Certis, US under the name Double Nickel TM obtained, accession number FERM BP-8234 and described in US Patent No. 7,094,592); (A1.3) Bacillus pumilus, in particular strain BU F-33 (accession number NRRL 50185); (A1.4) Bacillus subtilis var. amyloliquefaciens strain FZB24 (available from Novozymes, US under the name obtained); (A1.5) Paenibacillus sp. strains, accession number NRRL B-50972 or accession number NRRL B-67129, and described in International Patent Publication No. WO2016 / 154297; and

[0465] (A2) Fungi, such as (A2.1) Aureobasidium pullulans, in particular blastospores of strain DSM14940; (A2.2) blastospores of Aureobasidium pullulans of strain DSM 14941; (A2.3) a mixture of blastospores of Aureobasidium pullulans, in particular strains DSM14940 and DSM14941;

[0466] (B) Fungicides selected from the following:

[0467] (B1) Bacteria, for example (B1.1) Bacillus subtilis, in particular strain QST713 / AQ713 (available from Bayer CropScience LP, US under the name SERENADE OPTI or SERENADE ASO, accession number NRRL B21661 and described in US Patent No. 6,060,051); (B1.2) Bacillus pumilus, in particular strain QST2808 (available from Bayer CropScience LP, US under the name Obtained, accession number NRRL B-30087 and described in U.S. Patent No. 6,245,551); (B1.3) Bacillus pumilus, especially strain GB34 (available from Bayer AG, DE under Yield Obtained); (B1.4) Bacillus pumilus, especially strain BU F-33 (accession number NRRL 50185); (B1.5) Bacillus amyloliquefaciens, especially strain D747 (available from Certis, US under Double Nickel TM Obtained, accession number FERM BP-8234 and disclosed in U.S. Patent No. 7,094,592); (B1.6) Bacillus subtilis Y1336 (available from Bion-Tech in Taiwan, China under WP, registered as a biopesticide in Taiwan, China under accession numbers 4764, 5454, 5096 and 5277); (B1.7) Bacillus amyloliquefaciens strain MBI 600 (available from BASF SE under SUBTILEX); (B1.8) Bacillus subtilis strain GB03 (available from Bayer AG, DE under Obtained); (B1.9) Bacillus subtilis var. amyloliquefaciens strain FZB24 (available from Novozymes Biologicals Inc., Salem, Virginia or Syngenta Crop Protection, LLC, Greensboro, North Carolina under the fungicide Or ECO (EPA registration number 70127-5) obtained); (B1.10) Bacillus mycoides, isolate J (available from Certis USA under BmJ TGAI or WG); (B1.11) Bacillus licheniformis, especially strain SB3086 (available from Novozymes under EcoGuard TMBiofungicide and Green Releaf); (B1.12) Paenibacillus sp. strains, accession number NRRL B-50972 or accession number NRRL B-67129, and described in International Patent Publication No. WO 2016 / 154297.

[0468] In some embodiments, the biocontrol agent is a Bacillus subtilis or Bacillus amyloliquefaciens strain that produces fengycin or plipastatin-type compounds, iturin-type compounds, and / or surfactin-type compounds. For background, see the following review article: Ongena, M., et al., “Bacillus Lipopeptides: Versatile Weapons for Plant Disease Biocontrol,” Trends in Microbiology, Vol. 16, No. 3, March 2008, pp. 115-125. Bacillus strains capable of producing lipopeptides include Bacillus subtilis QST713 (available from Bayer CropScience LP, US as SERENADE OPTI or SERENADE ASO, accession number NRRL B21661 and described in U.S. Patent No. 6,060,051), Bacillus amyloliquefaciens strain D747 (available from Certis, US as DoubleNickel TM obtained, accession number FERM BP-8234 and disclosed in U.S. Patent No. 7,094,592); Bacillus subtilis MBI600 (available from Becker Underwood, US as obtained, EPA registration number 71840-8); Bacillus subtilis Y1336 (available from Bion-Tech in Taiwan, China as WP, registered as a biopesticide in Taiwan, China under accession numbers 4764, 5454, 5096, and 5277); Bacillus amyloliquefaciens, particularly strain FZB42 (available from ABiTEP, DE as obtained); and Bacillus subtilis var. amyloliquefaciens FZB24 (available from Novozymes Biologicals Inc., Salem, Virginia or Syngenta Crop Protection, LLC, Greensboro, North Carolina as the fungicide or ECO (EPA registration number 70127-5); and

[0469] (B2) Fungi, such as: (B2.1) Coniothyrium minitans, particularly strain CON / M / 91-8 (accession number DSM-9660; e.g., purchased from Bayer's ); (B2.2) Metschnikowia fructicola, especially strain NRRL Y-30752 (e.g. ); (B2.3) Microsphaeropsis ochracea (e.g. obtained from Prophyta ); (B2.5) Trichoderma spp., including Trichoderma atroviride, strain SC1 described in international application number PCT / IT2008 / 000196; (B2.6) Trichoderma harzianum rifai strain KRL-AG2 (also known as strain T-22, / ATCC 208479, e.g. obtained from BioWorks, US, PLANTSHIELD T-22G, and TurfShield); (B2.14) Gliocladium roseum, strain 321U obtained from W.F. Stoneman Company LLC; (B2.35) Talaromyces flavus, strain V117b; (B2.36) Trichoderma asperellum, strain ICC 012 obtained from Isagro; (B2.37) Trichoderma asperellum, strain SKT-1 (e.g. obtained from Kumiai Chemical Industry ); (B2.38) Trichoderma atroviride, strain CNCM I-1237 (e.g. obtained from Agrauxine, FR (WP); (B2.39) Trichoderma atroviride, strain number V08 / 002387; (B2.40) Trichoderma atroviride, strain NMI number V08 / 002388; (B2.41) Trichoderma atroviride, strain NMI number V08 / 002389; (B2.42) Trichoderma atroviride, strain NMI number V08 / 002390; (B2.43) Trichoderma atroviride, strain LC52 (such as Tenet provided by Agrimm Technologies Limited); (B2.44) Trichoderma atroviride, strain ATCC20476 (IMI 206040); (B2.45) Trichoderma atroviride, strain T11 (IMI352941 / CECT20498); (B2.46); Trichoderma harmatum; (B2.47) Trichoderma harzianum; (B2.48) Trichoderma harzianum rifai T39 (such as purchased from Makhteshim, US); (B2.49) Trichoderma harzianum, especially strain KD (such as Trichoplus (obtained by Becker Underwood) purchased from Biological Control Products, SA); (B2.50) Trichoderma harzianum, strain ITEM 908 (such as Trianum-P purchased from Koppert); (B2.51) Trichoderma harzianum, strain TH35 (such as Root-Pro provided by Mycontrol); (B2.52) Trichoderma virens (also known as Gliocladium virens), especially strain GL-21 (such as SoilGard 12G provided by Certis, US); (B2.53) Trichoderma viride, strain TV1 (such as Trianum-P provided by Koppert); (B2.54) Ampelomyces quisqualis, especially strain AQ 10 (such as AQ purchased from IntrachemBio Italia); (B2.56) Aureobasidium pullulans, especially blastospores of strain DSM14940; (B2.57) Aureobasidium pullulans, especially blastospores of strain DSM14941; (B2.58) A mixture of blastospores of Aureobasidium pullulans, especially strains DSM14940 and DSM 14941 (such as provided by bio-ferm, CH ); (B2.64) Cladosporium cladosporioides, strain H39 (provided by Stichting Dienst Landbouwkundig Onderzoek); (B2.69) Gliocladium catenulatum (synonym: Clonostachys rosea f. catenulate), strain J1446 (e.g., provided by AgBio Inc. and e.g., provided by Kemira Agro Oy ); (B2.70) conidia of Lecanicillium lecanii (previously known as: Verticillium lecanii), strain KV01 (e.g., provided by Koppert / Arysta ); (B2.71) Penicillium vermiculatum; (B2.72) Pichia anomala, strain WRL-076 (NRRL Y-30842); (B2.75) Trichoderma atroviride, strain SKT-1 (FERM P-16510); (B2.76) Trichoderma atroviride, strain SKT-2 (FERM P-16511); (B2.77) Trichoderma atroviride, strain SKT-3 (FERM P-17021); (B2.78) Trichoderma gamsii (formerly T. viride), strain ICC080 (IMICC 392151CABI, e.g., BioDerma provided by AGROBIOSOL DE MEXICO, S.A. DE C.V.); (B2.79) Trichoderma harzianum, strain DB 103 (e.g., T-Gro 7456 provided by Dagutat Biolab); (B2.80) Trichoderma polysporum, strain IMI 206039 (e.g., Binab TF WP provided by BINAB Bio-Innovation AB, Sweden); (B2.81) Trichoderma stromaticum (e.g., Tricovab provided by Ceplac, Brazil); (B2.83) Ulocladium oudemansii, especially strain HRU3 (e.g., provided by Botry-Zen Ltd, NZ ); (B2.84) Verticillium albo - atrum (formerly V. dahliae), strain WCS850 (CBS 276.92; e.g., Dutch Trig supplied by Tree Care Innovations); (B2.86) Verticillium chlamydosporium; (B2.87) a mixture of Trichoderma asperellum strain ICC 012 and Trichoderma gamsii strain ICC 080 (e.g., a product commercially available from Bayer CropScience LP, known as BIO - TAM in the US TM ).

[0470] Other examples of biocontrol agents that can be combined with the compounds of formula (I) or formula (II) and compositions containing them are:

[0471] Bacteria selected from the following: Bacillus cereus, in particular Bacillus cereus strain CNCM I-1562 and Bacillus firmus, strain I-1582 (registration number CNCM I-1582), Bacillus subtilis strain OST 30002 (registration number NRRL B-50421), Bacillus thuringiensis, in particular Bacillus thuringiensis subspecies israelensis (serotype H-14), strain AM65-52 (registration number ATCC 1276), Bacillus thuringiensis subsp. aizawai, in particular strain ABTS-1857 (SD-1372), Bacillus thuringiensis subsp. kurstaki strain HD-1, Bacillus thuringiensis subsp. tenebrionis strain NB 176 (SD-5428), Pasteuria penetrans, Pasteuria spp. (Rotylenchulus reniformis nematode)-PR3 (registration number ATCC SD-5834), Streptomyces microflavus strain AQ6121 (= QRD 31.013, NRRL B-50550), Streptomyces galbus strain AQ 6047 (registration number NRRL 30232).

[0472] Fungi and yeasts selected from the following: Beauveria bassiana, in particular strain ATCC 74040; Lecanicillium spp., in particular strain HRO LEC 12; Metarhizium anisopliae, in particular strain F52 (DSM 3884 or ATCC 90448); Paecilomyces fumosoroseus (now: Isaria fumosorosea), in particular strain IFPC 200613 or strain Apopka 97 (registration number ATCC 20874); and Paecilomyces lilacinus, in particular Paecilomyces lilacinus strain 251 (AGAL 89 / 030550);

[0473] Viruses selected from the following: Adoxophyes orana (summer fruit tortrix) granulovirus (GV), Cydia pomonella (codling moth) granulovirus (GV), Helicoverpa armigera (cotton bollworm) nucleopolyhedrovirus (NPV), Spodoptera exigua (beet armyworm) mNPV, Spodoptera frugiperda (fall armyworm) mNPV and Spodoptera littoralis (African cotton leafworm) NPV.

[0474] Bacteria and fungi that can be added as an "inoculant" to a plant or plant part or plant organ and that, by virtue of their specific properties, promote plant growth and plant health. Examples are: Agrobacterium spp., Azorhizobium caulinodans, Azospirillum spp., Azotobacter spp., Bradyrhizobium spp., Burkholderia spp., in particular Burkholderia cepacia (formerly Pseudomonas cepacia), Gigaspora spp. or Gigasporamonosporum, Glomus spp., Laccaria spp., Lactobacillus buchneri, Paraglomus spp., Pisolithus tinctorus, Pseudomonas spp., Rhizobium spp., in particular Rhizobium trifolii, Rhizopogon spp., Scleroderma spp., Suillus spp. and Streptomyces spp.

[0475] Plant extracts and products formed by microorganisms (including proteins and secondary metabolites) that can be used as biocontrol agents are: for example, garlic (Allium sativum), wormwood (Artemisia absinthium), azadirachtin, Biokeeper WP, Cassia nigricans, Celastrus angulatus, Chenopodium anthelminticum, chitin, Armour-Zen, Dryopteris filix-mas, Equisetum arvense, Fortune Aza, Fungastop, Heads Up (Chenopodium quinoa saponin extract), pyrethrum / pyrethrins, Quassia amara, Quercus, Quillaja, Regalia, "Requiem TM Insecticides", rotenone, ryania / ryanodine, Symphytum officinale, Tanacetum vulgare, thymol, Triact 70, TriCon, Tropaeulum majus, Urtica dioica, Veratrin, Viscum album, Brassicaceae extracts (especially rapeseed powder or mustard powder).

[0476] Examples of insecticides, acaricides and nematicides that can each be mixed with the compounds of formula (I) or formula (II) and compositions containing them are:

[0477] (1) Acetylcholinesterase (AChE) inhibitors, such as carbamates, such as alanycarb, bendiocarb, benfuracarb, butocarboxim, butoxycarboxim, carbaryl, carbosulfan, ethiofencarb, fenobucarb, formetanate, furathiocarb, isoprocarb, methiocarb, metolcarb, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, triazamate, trimethacarb, XMC, and xylylcarb, or organophosphates,For example, acephate, azamethiphos, azinphos-ethyl, azinphos-methyl, chlorethoxyfos, chlorfenvinphos, chlormephos, chlorpyrifos-methyl, cyanophos, demeton-S-methyl, diazinon, dichlorvos / DDVP, dicrotophos, dimethoate, dimethylvinphos, disulfoton, EPN, ethion, famphur, fenitrothion, fenthion, fosthiazate, heptenophos, imicyafos, isofenphos, isopropyl O-(methoxyaminothiophosphoryl) salicylate, isoxathion, malathion, mecarbam, mevinphos, naled, oxydemeton-methyl, phenthoate, phosalone, phosmet, phoxim, pirimiphos-methyl, profenofos, propetamphos, prothiofos, pyraclofos, pyridaphenthion, quinalphos, tebupirimfos, temephos, tetrachlorvinphos, thiometon, triazophos, triclorfon and vamidothion.,

[0478] (2) GABA-gated chloride channel blockers, such as cyclodiene organochlorines, or fiproles, such as ethiprole and fipronil.

[0479] (3) Sodium channel modulators, such as pyrethroids, such as acrinathrin, allethrin, d-cis-trans allethrin, d-trans allethrin, bifenthrin, bioallethrin, bioallethrin S-cyclopentenyl isomer, resmethrin, cycloprothrin, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, gamma-cyhalothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, theta-cypermethrin, zeta-cypermethrin, cyphenothrin [(1R)-trans isomer], deltamethrin, empenthrin [(EZ)-(1R) isomer], esfenvalerate, etofenprox, fenpropathrin, fenvalerate, flucythrinate, flumethrin, tau-fluvalinate, halfenprox, imiprothrin, kadethrin, momfluorothrin, permethrin, phenothrin [(1R)-trans isomer], prallethrin, pyrethrins (pyrethrum), resmethrin, silafluofen, tefluthrin, tetramethrin, tetramethrin [(EZ)-(1R)-isomer], tralomethrin, and transfluthrin, or methoxychlor.

[0480] (4) Nicotinic acetylcholine receptor (nAChR) competitive modulators, such as neonicotinoids, such as acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram, thiacloprid, and thiamethoxam, or nicotine, or sulfoxaflor, or flupyradifurone.

[0481] (5) Nicotinic acetylcholine receptor (nAChR) allosteric modulators, such as spinosyns, such as spinetoram and spinosad.

[0482] (6) Glutamate-gated chloride channel (GluCl) allosteric modulators, such as avermectins / milbemycins, such as abamectin, emamectin benzoate, lepimectin, and milbemectin.

[0483] (7) Juvenile hormone mimics, such as juvenile hormone analogs, such as hydroprene, kinoprene, and methoprene, or fenoxycarb, or pyriproxyfen.

[0484] (8) Other non-specific (multisite) inhibitors, such as alkyl halides, such as methyl bromide and other alkyl halides; or chloropicrine or sulphuryl fluoride or borax or tartar emetic or methyl isocyanate generators, such as dazomet and metam.

[0485] (9) Chordotonal Organ modulators, such as pymetrozine or flonicamide.

[0486] (10) Mite growth inhibitors, such as clofentezine, hexythiazox, diflovidazin, or etoxazole.

[0487] (11) Insect midgut microbiota disruptors, such as Bacillus thuringiensis subspecies israelensis, Bacillus sphaericus, Bacillus thuringiensis subspecies aizawai, Bacillus thuringiensis subspecies kurstaki, Bacillus thuringiensis subspecies tenebrionis, and B.t plant proteins: Cry1Ab, Cry1Ac, Cry1Fa, Cry1A.105, Cry2Ab, Vip3A, mCry3A, Cry3Ab, Cry3Bb, Cry34Ab1 / 35Ab1.

[0488] (12) Mitochondrial ATP synthase inhibitors, such as ATP disruptors, such as diafenthiuron, or organotin compounds, such as azocyclotin, cyhexatin, and fenbutatin oxide, or propargite, or tetradifon.

[0489] (13) Uncouplers of oxidative phosphorylation by disrupting the proton gradient, such as chlorfenapyr and DNOC.

[0490] (14) Nicotinic acetylcholine receptor channel blockers, such as bensultap, cartap hydrochloride, thiocyclam, and thiosultap-sodium.

[0491] (15)Type 0 chitin biosynthesis inhibitors, such as bistrifluron, chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, teflubenzuron, and triflumuron.

[0492] (16)Type 1 chitin biosynthesis inhibitors, such as buprofezin.

[0493] (17)Ecdysis disruptors (especially for Diptera, i.e., dipteran insects), such as cyromazine.

[0494] (18)Ecdysteroid receptor agonists, such as chromafenozide, halofenozide, methoxyfenozide, and tebufenozide.

[0495] (19)Octopamine receptor agonists, such as amitraz.

[0496] (20)Mitochondrial complex III electron transport inhibitors, such as hydramethylnone, acequinocyl, or fluacrypyrim.

[0497] (21)Mitochondrial complex I electron transport inhibitors, such as METI acaricides, such as fenazaquin, fenpyroximate, pyrimidifen, pyridaben, tebufenpyrad, and tolfenpyrad, or rotenone (Derris).

[0498] (22)Voltage-dependent sodium channel blockers, such as indoxacarb or metaflumizone.

[0499] (23) Acetyl coenzyme A (CoA) carboxylase inhibitors, such as tetronic acid and tetramic acid derivatives, such as spirodiclofen, spiromesifen, and spirotetramat.

[0500] (24) Mitochondrial complex IV electron transport inhibitors, such as phosphines, such as phosphine, or cyanides, such as calcium cyanide, potassium cyanide, and sodium cyanide.

[0501] (25) Mitochondrial complex II electron transport inhibitors, such as beta-ketonitrile derivatives, such as cyenopyrafen and cyflumetofen, and carboxanilides, such as pyflubumide.

[0502] (28) Ryanodine receptor modulators, such as diamides, such as chlorantraniliprole, cyantraniliprole, and flubendiamide,

[0503] Other active compounds, such as afidopyropen, afoxolaner, azadirachtin, benclothiaz, benzoximate, bifenazate, broflanilide, bromopropylate, chinomethionat, chloroprallethrin, cryolite, cyclaniliprole, cycloxaprid, cyhalodiamide, dicloromezotiaz, epsilon metofluthrin, epsilon-Momfluthrin, flometoquin, fluazaindolizine, fluensulfone, flufenerim, flufenoxystrobin, flufiprole, fluhexafon, fluopyram, fluralaner, fluxametamide, fufenozide, guadipyr, heptafluthrin, imidaclothiz, iprodione, kappa-bifenthrin, kappa-tefluthrin, lotilaner, meperfluthrin, paichongding, pyridalyl, pyrifluquinazon, pyriminostrobin, spirobudiclofen, tetramethylfluthrin, tetraniliprole, tetrachlorantraniliprole, tiigolaner, tioxazafen, thiofluoximate, triflumezopyrim, and iodomethane; other Bacillus firmus-based preparations (I-1582, BioNeem, Votivo), and the following compounds: 1-{2-fluoro-4-methyl-5-[(2,2,{[2-(Trifluoroethyl)sulfinyl]phenyl}-3-(trifluoromethyl)-1H-1,2,4-triazol-5-amine (known from WO2006 / 043635) (CAS 885026-50-6), {1'-[(2E)-3-(4-chlorophenyl)prop-2-en-1-yl]-5-fluorospiro[indole-3,4'-piperidine]-1(2H)-yl}(2-chloropyridin-4-yl)methanone (known from WO2003 / 106457) (CAS 637360-23-7), 2-chloro-N-[2-{1-[(2E)-3-(4-chlorophenyl)prop-2-en-1-yl]piperidin-4-yl}-4-(trifluoromethyl)phenyl]isonicotinamide (known from WO2006 / 003494) (CAS 872999-66-1), 3-(4-chloro-2,6-dimethylphenyl)-4-hydroxy-8-methoxy-1,8-diazaspiro[4.5]dec-3-en-2-one (known from WO 2010052161) (CAS1225292-17-0), 3-(4-chloro-2,6-dimethylphenyl)-8-methoxy-2-oxo-1,8-diazaspiro[4.5]dec-3-en-4-yl ethyl carbonate (known from EP2647626) (CAS-1440516-42-6), 4-(but-2-yn-1-yloxy)-6-(3,5-dimethylpiperidin-1-yl)-5-fluoropyrimidine (known from WO2004 / 099160) (CAS 792914-58-0), PF1364 (known from JP2010 / 018586) (CAS Registry No. 1204776-60-2), N-[(2E)-1-[(6-chloropyridin-3-yl)methyl]pyridin-2(1H)-ylidene]-2,2,2-trifluoroacetamide (known from WO2012 / 029672) (CAS 1363400-41-2), (3E)-3-[1-[(6-chloro-3-pyridinyl)methyl]-2-pyridinylidene]-1,1,1-trifluoro-propan-2-one (known from WO2013 / 144213) (CAS1461743-15-6), N-[3-(benzylcarbamoyl)-4-chlorophenyl]-1-methyl-3-(pentafluoroethyl)-4-(trifluoromethyl)-1H-pyrazole-5-carboxamide (known from WO2010 / 051926) (CAS1226889-14-0), 5-bromo-4-chloro-N-[4-chloro-2-methyl-6-(methylcarbamoyl)phenyl]-2-(3-chloropyridin-2-yl)pyrazole-3-carboxamide (known from CN103232431) (CAS1449220-44-3), 4-[5-(3,5-dichlorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-2-methyl-N-(cis-1-oxido-3-thietanyl)benzamide, 4-[5-(3,5-(3,5-dichlorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-2-methyl-N-(trans-1-oxido-3-thietanyl)benzamide and 4-[(5S)-5-(3,5-dichlorophenyl)-4,5-dihydro-5-(trifluoromethyl)-3-isoxazolyl]-2-methyl-N-(cis-1-oxido-3-thietanyl)benzamide (known from WO 2013 / 050317 A1) (CAS 1332628-83-7), N-[3-chloro-1-(3-pyridinyl)-1H-pyrazol-4-yl]-N-ethyl-3-[(3,3,3-trifluoropropyl)sulfinyl]propanamide, (+)-N-[3-chloro-1-(3-pyridinyl)-1H-pyrazol-4-yl]-N-ethyl-3-[(3,3,3-trifluoropropyl)sulfinyl]propanamide and (-)-N-[3-chloro-1-(3-pyridinyl)-1H-pyrazol-4-yl]-N-ethyl-3-[(3,3,3-trifluoropropyl)sulfinyl]propanamide (known from WO 2013 / 162715 A2, WO 2013 / 162716 A2, US 2014 / 0213448 A1) (CAS 1477923-37-7), 5-[[(2E)-3-chloro-2-propen-1-yl]amino]-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-4-[(trifluoromethyl)sulfinyl]-1H-pyrazole-3-carbonitrile (known from CN 101337937 A) (CAS 1105672-77-2), 3-bromo-N-[4-chloro-2-methyl-6-[(methylamino)thiomethyl]phenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamide, (Liudaibenjiaxuanan, known from CN 103109816 A) (CAS 1232543-85-9); N-[4-chloro-2-[[(1,1-dimethylethyl)amino]carbonyl]-6-methylphenyl]-1-(3-chloro-2-pyridinyl)-3-(fluoromethoxy)-1H-pyrazole-5-carboxamide (known from WO 2012 / 034403 A1) (CAS 1268277-22-0), N-[2-(5-amino-1,3,4-thiadiazol-2-yl)-4-chloro-6-methylphenyl]-3-bromo-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamide (known from WO 2011 / 085575 A1) (CAS 1233882-22-8), 4-[3-[2,6-dichloro-4-[(3,3-(dichloro-2-propen-1-yloxy)phenoxy]propoxy]-2-methoxy-6-(trifluoromethyl)-pyrimidine (known from CN 101337940 A) (CAS 1108184-52-6); (2E)-2-[2-(4-cyanophenyl)-1-[3-(trifluoromethyl)phenyl]ethylidene]-N-[4-(difluoromethoxy)phenyl]hydrazinecarboxamide and 2(Z)-2-[2-(4-cyanophenyl)-1-[3-(trifluoromethyl)phenyl]ethylidene]-N-[4-(difluoromethoxy)phenyl]hydrazinecarboxamide (known from CN 101715774 A) (CAS 1232543-85-9); 3-(2,2-dichlorovinyl)-2,2-dimethyl-4-(1H-benzimidazol-2-yl)phenyl-cyclopropanecarboxylate (known from CN 103524422 A) (CAS 1542271-46-4); (4aS)-7-chloro-2,5-dihydro-2-[[(methoxycarbonyl)[4-[(trifluoromethyl)thio]phenyl]amino]carbonyl]-indeno[1,2-e][1,3,4]diazine-4a(3H)-carboxylic acid methyl ester (known from CN 102391261 A) (CAS 1370358-69-2); 6-deoxy-3-O-ethyl-2,4-di-O-methyl 1-[N-[4-[1-[4-(1,1,2,2,2-pentafluoroethoxy)phenyl]-1H-1,2,4-triazol-3-yl]phenyl]carbamate]-α-L-mannopyranose (known from US2014 / 0275503 A1) (CAS 1181213-14-8); 8-(2-cyclopropylmethoxy-4-trifluoromethylphenoxy)-3-(6-trifluoromethylpyridazin-3-yl)-3-azabicyclo[3.2.1]octane (CAS 1253850-56-4), (8-trans)-8-(2-cyclopropylmethoxy-4-trifluoromethylphenoxy)-3-(6-trifluoromethylpyridazin-3-yl)-3-azabicyclo[3.2.1]octane (CAS 933798-27-7), (8-cis)-8-(2-cyclopropylmethoxy-4-trifluoromethylphenoxy)-3-(6-trifluoromethylpyridazin-3-yl)-3-azabicyclo[3.2.1]octane (known from WO 2007040280A1, WO 2007040282A1) (CAS 934001-66-8), N-[3-chloro-1-(3-pyridyl)-1H-pyrazol-4-yl]-N-ethyl-3-[(3,3,3-(Trifluoropropyl)thio]propanamide (known from WO 2015 / 058021 A1, WO 2015 / 058028 A1) (CAS 1477919-27-9) and N-[4-(Aminothiomethyl)-2-methyl-6-[(methylamino)carbonyl]phenyl]-3-bromo-1-(3-chloro-2-pyridyl)-1H-pyrazole-5-carboxamide (known from CN103265527 A) (CAS1452877-50-7), 5-(1,3-Dioxolan-2-yl)-4-[[4-(trifluoromethyl)phenyl]methoxy]-pyrimidine (known from WO 2013 / 115391 A1) (CAS 1449021-97-9), 3-(4-Chloro-2,6-dimethylphenyl)-4-hydroxy-8-methoxy-1-methyl-1,8-diazaspiro[4.5]dec-3-en-2-one (known from WO 2010 / 066780A1, WO 2011 / 151146A1) (CAS1229023-34-0), 3-(4-Chloro-2,6-dimethylphenyl)-8-methoxy-1-methyl-1,8-diazaspiro[4.5]decane-2,4-dione (known from WO 2014 / 187846 A1) (CAS1638765-58-8), 3-(4-Chloro-2,6-dimethylphenyl)-8-methoxy-1-methyl-2-oxo-1,8-diazaspiro[4.5]dec-3-en-4-yl ethyl carbonate (known from WO 2010 / 066780A1, WO 2011151146 A1) (CAS1229023-00-0), N-[1-[(6-Chloro-3-pyridyl)methyl]-2(1H)-pyridinylidene]-2,2,2-trifluoroacetamide (known from DE 3639877 A1, WO2012029672A1) (CAS1363400-41-2), [N(E)]-N-[1-[(6-Chloro-3-pyridyl)methyl]-2(1H)-pyridinylidene]-2,2,2-trifluoroacetamide (known from WO 2016005276A1) (CAS1689566-03-7), [N(Z)]-N-[1-[(6-Chloro-3-pyridyl)methyl]-2(1H)-pyridinylidene]-2,2,2-trifluoroacetamide (CAS1702305-40-5), 3-endo-3-[2-Propoxy-4-(trifluoromethyl)phenoxy]-9-[[5-(trifluoromethyl)-2-pyridyl]oxy]-9-azabicyclo[3.3.1]nonane (known from WO 2011 / 105506 A1, WO 2016 / 133011A1) (CAS1332838-17-1).

[0504] Examples of safeners that can be mixed with the compounds of formula (I) or (II) and compositions containing them are, for example, benoxacor, cloquintocet (-mexyl), cyometrinil, cyprosulfamide, dichlormid, fenchlorazole (-ethyl), fenclorim, flurazole, fluxofenim, furilazole, isoxadifen (-ethyl), mefenpyr (-diethyl), naphthalic anhydride, oxabetrinil, 2-methoxy-N-({4-[(methylcarbamoyl)amino]phenyl}sulfonyl)benzamide (CAS 129531-12-0), 4-(dichloroacetyl)-1-oxa-4-azaspiro[4.5]decane (CAS 71526-07-3), 2,2,5-trimethyl-3-(dichloroacetyl)-1,3-oxazolidine (CAS 52836-31-4).

[0505] Examples of herbicides that can be mixed with the compounds of formula (I) or (II) and compositions containing them are:

[0506] acetochlor, acifluorfen, acifluorfen-sodium, aclonifen, alachlor, allidochlor, alloxydim, alloxydim-sodium, ametryn, amicarbazone, amidochlor, amidosulfuron, 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methylphenyl)-5-fluoropyridine-2-carboxylic acid, aminocyclopyrachlor, aminocyclopyrachlor-potassium, aminocyclopyrachlor-methyl, aminopyralid, amitrole, ammonium sulfamate, anilofos, asulam, atrazine, azafenidin, azimsulfuron, beflubutamid, benazolin, benazolin-ethyl, benfluralin, benfuresate, bensulfuron, bensulfuron-methyl, bensulide, bentazone, benzobicyclon, benzofenap, bicyclopyron, bifenox, bialaphos, bilanafos-sodium, bispyribac, bispyribac-sodium, bromacil, bromobutide, bromofenoxim, bromoxynil, bromoxynil-butyrate, bromoxynil-potassium, bromoxynil-heptanoate, and bromoxynil-octanoate, busoxinoneButachlor, butafenacil, butamifos, butenachlor, butralin, butroxydim, butylate, cafenstrole, carbetamide, carfentrazone, carfentrazone-ethyl, chloramben, chlorbromuron, chlorfenac, chlorfenac-sodium, chlorfenprop, chlorflurenol, chlorflurenol-methyl, chloridazon, chlorimuron, chlorimuron-ethyl, chlorophthalim, chlorotoluron, chlorthal-dimethyl, cinidon, cinidon-ethyl, cinmethylin, cinosulfuron, clacyfos, clethodim, clodinafop, clodinafop-propargyl, clomazone, clomeprop, clopyralid, cloransulam, cloransulam-methyl, cumyluron, cyanamide, cyanazine, cycloate, cyclopyrimorate, cyclosulfamuron, cycloxydim, cyhalofop, cyhalofop-butyl, cyprazine, 2,4-D, 2,4-D-butoyl, 2,4-D-butyl ester, 2,4-D-dimethylammonium, 2,4-D-diolamine, 2,4-D-ethyl ester, 2,4-D-2-ethylhexyl ester, 2,4-D-isobutyl ester, 2,4-D-isooctyl ester, 2,4-D-isopropylammonium, 2,4-D-potassium,2,4-D-triisopropanolammonium and 2,4-D-trolamine, 2,4-DB, 2,4-DB-butyl ester, 2,4-DB-dimethylammonium, 2,4-DB-isooctyl ester, 2,4-DB-potassium and 2,4-DB-sodium, daimuron (dymron), dalapon, dazomet, n-decanol, desmedipham, detosyl-pyrazolate (DTP), dicamba, dichlobenil, 2-(2,4-dichlorobenzyl)-4,4-dimethyl-1,2-oxazolidin-3-one, 2-(2,5-dichlorobenzyl)-4,4-dimethyl-1,2-oxazolidin-3-one, dichlorprop, dichlorprop-P, diclofop, diclofop-methyl, diclofop-P-methyl, diclosulam, difenzoquat, diflufenican, diflufenzopyr, diflufenzopyr-sodium, dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethenamid, dimethenamid-P, dimetrasulfuron, dinitramine, dinoterb, diphenamid, diquat, diquat-dibromide, dithiopyr, diuron, DNOC, endothal, EPTC, esprocarb, ethalfluralin, ethametsulfuron-methyl, ethiozin, ethofumesate, ethoxyfen, ethoxyfen-ethyl, ethoxysulfuron, etobenzanid, F-9600,F-5231, namely N-[2-chloro-4-fluoro-5-[4-(3-fluoropropyl)-5-oxo-4,5-dihydro-1H-tetrazol-1-yl]phenyl]ethanesulfonamide, F-7967, namely 3-[7-chloro-5-fluoro-2-(trifluoromethyl)-1H-benzoimidazol-4-yl]-1-methyl-6-(trifluoromethyl)pyrimidine-2,4(1H,3H)-dione, fenoxaprop, fenoxaprop-P, fenoxaprop-ethyl, fenoxaprop-P-ethyl, fenoxasulfone, fenquinotrione, fentrazamide, flamprop, flamprop-M-isopropyl, flamprop-M-methyl, flazasulfuron, florasulam, fluazifop, fluazifop-P, fluazifop-butyl, fluazifop-P-butyl, flucarbazone, flucarbazone-sodium, flucetosulfuron, fluchloralin, flufenacet, flufenpyr, flufenpyr-ethyl, flumetsulam, flumiclorac, flumiclorac-pentyl, flumioxazin, fluometuron, 9-hydroxyfluorene carboxylic acid, flurenol-butyl, flurenol-dimethylammonium, flurenol-methyl, fluoroglycofen, fluoroglycofen-ethyl, flupropanate, flupyrsulfuron, flupyrsulfuron-methyl-sodium, fluridone, flurochloridone, fluroxypyrfluroxypyr-meptyl, flurtamone, fluthiacet, fluthiacet-methyl, fomesafen, fomesafen-sodium, foramsulfuron, fosamine, glufosinate, glufosinate-ammonium, glufosinate-P-sodium, glufosinate-P-ammonium, glufosinate-P-sodium, glyphosate, glyphosate-ammonium, glyphosate-isopropylammonium, glyphosate-diammonium, glyphosate-dimethylammonium, glyphosate-potassium, glyphosate-sodium, glyphosate-trimesium, H-9201, namely O-(2,4-dimethyl-6-nitrophenyl) O-ethyl isopropylphosphoramidothioate, halauxifen, halauxifen-methyl, halosafen, halosulfuron, halosulfuron-methyl, haloxyfop, haloxyfop-P, haloxyfop-ethoxyethyl, haloxyfop-P-ethoxyethyl, haloxyfop-methyl, haloxyfop-P-methyl, hexazinone, HW-02, namely ethyl-(2,4-dichlorophenoxy) acetate 1-(dimethoxyphosphoryl) ester, imazamethabenz,Imazamethabenz-methyl, imazamox, imazamox-ammonium, imazapic, imazapic-ammonium, imazapyr, imazapyr-isopropylammonium, imazaquin, imazaquin-ammonium, imazethapyr, imazethapyr-immonium, imazosulfuron, indanofan, indaziflam, iodosulfuron, iodosulfuron-methyl-sodium, ioxynil, ioxynil-octanoate, ioxynil-potassium, and ioxynil-sodium, ipfencarbazone, isoproturon, isouron, isoxaben, isoxaflutole, karbutilate, KUH-043, namely 3-({[5-(difluoromethyl)-1-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl]methyl}sulfonyl)-5,5-dimethyl-4,5-dihydro-1,2-oxazole, ketospiradox, lactofen, lenacil, linuron, MCPA, MCPA-butotyl, MCPA-dimethylammonium, MCPA-2-ethylhexyl ester, MCPA-isopropylammonium, MCPA-potassium, MCPA-sodium, MCPB, MCPB-methyl ester, MCPB-ethyl ester, MCPB-sodium, mecoprop, mecoprop-sodium, mecoprop-butotyl, mecoprop-P, mecoprop-P-butotyl, mecoprop-P-dimethylammonium,Mecoprop-P-2-ethylhexyl, Mecoprop-P-potassium, Mefenacet, Mefluidide, Mesosulfuron, Mesosulfuron-methyl, Mesotrione, Methabenzthiazuron, Metam, Metamifop, Metamitron, Metazachlor, Metazosulfuron, Methabenzthiazuron, Methiopyrsulfuron, Methiozolin, Methyl isothiocyanate, Metobromuron, Metolachlor, S-Metolachlor, Metosulam, Metoxuron, Metribuzin, Metsulfuron, Molinate, Monolinuron, Monosulfuron, Monosulfuron-ester, MT-5950, namely N-[3-chloro-4-isopropylphenyl]-2-methylpentanamide, NGGC-011, Napropamide, NC-310, namely [5-benzyloxy-1-methyl-1H-pyrazol-4-yl](2,4-dichlorophenyl)methanone, Neburon, Nicosulfuron, Pelargonic acid, Norflurazon, Oleic acid (fatty acid), Orbencarb, Orthosulfamuron, Oryzalin, Oxadiargyl, Oxadiazon, Oxasulfuron, Oxaziclomefon, Oxyfluorfen, Paraquat dichloride, Pebulate, Pendimethalin, Penoxsulam, Pentachlorophenol, Pentoxazone, Pethoxamid, Mineral oil,phenmedipham, picloram, picolinafen, pinoxaden, piperophos, pretilachlor, primisulfuron, primisulfuron-methyl, prodiamine, profoxydim, prometon, prometryn, propachlor, propanil, propaquizafop, propazine, propham, propisochlor, propoxycarbazone, propoxycarbazone-sodium, propyrisulfuron, propyzamide, prosulfocarb, prosulfuron, pyraclonil, pyraflufen, pyraflufen-ethyl, pyrasulfotole, pyrazolynate (pyrazolate), pyrazosulfuron, pyrazosulfuron-ethyl, pyrazoxyfen, pyribambenz, pyribambenz-isopropyl, pyribambenz-propyl, pyribenzoxim, pyributicarb, pyridafol, pyridate, pyriftalid, pyriminobac, pyriminobac-methyl, pyrimisulfan, pyrithiobac, pyrithiobac-sodium, pyroxasulfone, pyroxsulam, quinclorac, quinmerac, quinoclamine, quizalofop, quizalofop-ethyl, quizalofop-Pquizalofop-P-ethyl, quizalofop-P-tefuryl, rimsulfuron, saflufenacil, sethoxydim, siduron, simazine, simetryn, SL-261, sulcotrion, sulfentrazone, sulfometuron, sulfometuron-methyl, sulfosulfuron, SYN-523, SYP-249, i.e., 1-ethoxy-3-methyl-1-oxobut-3-en-2-yl 5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrobenzoate, SYP-300, i.e., 1-[7-fluoro-3-oxo-4-(prop-2-yn-1-yl)-3,4-dihydro-2H-1,4-benzoxazin-6-yl]-3-propyl-2-thioxoimidazolidine-4,5-dione, 2,3,6-TBA, TCA (trichloroacetic acid), TCA-sodium, tebuthiuron, tefuryltrione, tembotrione, tepraloxydim, terbacil, terbucarb, terbumeton, terbuthylazin, terbutryn, thenylchlor, thiazopyr, thiencarbazone, thiencarbazone-methyl, thifensulfuron, thifensulfuron-methyl, thiobencarb, tiafenacil, tolpyralate, topramezone, tralkoxydim, triafamone, tri-allate, triasulfuron, triaziflam, tribenuron, tribenuron-methyl, triclopyr, trietazine, trifloxysulfuron, trifloxysulfuron-sodiumtrifludimoxazin, trifluralin, triflusulfuron, triflusulfuron-methyl, tritosulfuron, urea sulfate, vernolate, XDE-848, ZJ-0862, namely 3,4-dichloro-N-{2-[(4,6-dimethoxypyrimidin-2-yl)oxy]benzyl}aniline, and the following compounds:

[0507]

[0508] Examples of plant growth regulators are:

[0509] acibenzolar, acibenzolar-S-methyl, 5-aminolevulinic acid, ancymidol, 6-benzylaminopurine, brassinolide, catechine, chlormequat chloride, cloprop, cyclanilide, 3-(cycloprop-1-enyl)propanoic acid, daminozide, dazomet, n-decanol, dikegulac, dikegulac-sodium, endothal, endothal-dipotassium, endothal-disodium, and endothal mono(N,(N-dimethylalkylammonium), ethephon, flumetralin, flurenol, flurenol-butyl, flurprimidol, forchlorfenuron, gibberellic acid, inabenfide, indol-3-acetic acid (IAA), 4-indol-3-ylbutyric acid, isoprothiolane, probenazole, jasmonic acid, maleic hydrazide, mepiquat chloride, 1-methylcyclopropene, methyljasmonate, 2-(1-naphthyl)acetamide, 1-naphthylacetic acid, 2-naphoxyacetic acid, nitrophenolate mixture, paclobutrazol, N-(2-phenylethyl)-β-alanine, N-phenylphthalamic acid, prohexadione, prohexadione-calcium, prohydrojasmone, salicylic acid, strigolactone, tecnazene, thidiazuron, triacontanol, trinexapac, trinexapac-ethyl, tsitodef, uniconazole, uniconazole-P.,

[0510] Methods and uses

[0511] Compounds of formula (I) or formula (II) and compositions containing them have effective microbicidal activity. They can be used to control unwanted microorganisms, such as unwanted fungi and bacteria. They can be particularly used in crop protection (they control microorganisms causing plant diseases) or for protecting materials detailed below (such as, industrial materials, wood, stored goods). More specifically, compounds of formula (I) or formula (II) and compositions containing them can be used to protect seeds, germinated seeds, newly emerged seedlings, plants, plant parts, fruits, harvested items and / or the soil in which plants grow from unwanted microorganisms.

[0512] As used herein, "control" or "controlling" encompasses protective, therapeutic, and eradication treatments of unwanted microorganisms. The unwanted microorganisms can be pathogenic bacteria, pathogenic viruses, pathogenic oomycetes, or pathogenic fungi, more specifically plant pathogenic bacteria, plant pathogenic viruses, plant pathogenic oomycetes, or plant pathogenic fungi. As detailed below, these plant pathogenic microorganisms are the pathogens of broad-spectrum plant diseases.

[0513] More specifically, the compounds of formula (I) or formula (II) and compositions containing them can be used as fungicides. For the purposes of this specification, the term "fungicide" refers to such a compound or composition that can be used in crop protection to control unwanted fungi, such as Plasmodiophoromycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, and Deuteromycetes and / or to control oomycetes, more preferably to control Basidiomycetes (causing rust).

[0514] Accordingly, the present invention also relates to a method for controlling unwanted microorganisms, such as plant pathogenic fungi, oomycetes, and bacteria, which comprises the step of applying at least one compound of formula (I) or formula (II) or at least one composition containing it to the microorganisms and / or their habitats (applying to plants, plant parts, seeds, fruits, or the soil in which the plants grow).

[0515] Generally, when the compounds and compositions of the present invention are used in a therapeutic or protective method for controlling plant pathogenic fungi and / or plant pathogenic oomycetes, they are applied to plants, plant parts, fruits, seeds, or the soil or substrate in which the plants grow in an effective and plant-compatible amount. Suitable substrates for cultivating plants include inorganic substrates, such as mineral wool, especially asbestos, perlite, sand, or gravel; organic substrates, such as peat, pine bark, or sawdust; and petroleum-based substrates, such as polymer foams or plastic beads. The effective and plant-compatible amount means an amount sufficient to control or destroy the fungi present or likely to appear in the farmland and not to cause any obvious phytotoxic symptoms in the said crops. This amount can vary within a wide range, depending on the fungi to be controlled, the type of crop, the growth stage of the crop, the climatic conditions, and the individual compounds or compositions of the present invention used. This amount can be determined by systematic field trials within the capabilities of those skilled in the art.

[0516] Plants and plant parts

[0517] The compounds of formula (I) and compositions containing them can be applied to any plant or plant part.

[0518] "Plant" means all plants and plant populations, such as wanted and unwanted wild plants or crop plants (including naturally occurring crop plants). Crop plants can be plants obtained by conventional breeding and optimization methods or by biotechnological and genetic engineering methods or combinations of these methods, including genetically modified plants (GMOs or transgenic plants) and plant cultivars protected or not protected by plant breeders’ rights.

[0519] "Plant part" shall be understood to mean all parts and organs, whether above or below ground, of a plant, such as shoots, leaves, flowers and roots, examples of which include leaves, needles, stems, trunks, flowers, fruiting bodies, fruits, seeds, roots, tubers and rhizomes. Plant parts also include harvested material and asexual and sexual propagation material, such as cuttings, tubers, rhizomes, offsets and seeds.

[0520] Plants that can be processed according to the method of the present invention include the following: cotton, flax, grapevine, fruits, vegetables, such as Rosaceae sp. (e.g., pomaceous fruits, such as apples and pears, and stone fruits, such as apricots, cherries, almonds, and peaches, and small fruits, such as strawberries), Ribesioidae sp., Juglandaceae sp., Betulaceae sp., Anacardiaceae sp., Fagaceae sp., Moraceae sp., Oleaceaesp., Actinidaceaesp., Lauraceae sp., Musaceae sp. (e.g., banana trees and banana plantations), Rubiaceae sp. (e.g., coffee), Theaceae sp., Sterculiceae sp., Rutaceae sp. (e.g., lemons, oranges, and grapefruits), Solanaceae sp. (e.g., tomatoes), Liliaceae sp., Asteraceaesp. (e.g., lettuce), Umbelliferae sp., Cruciferae sp., Chenopodiaceae sp., Cucurbitaceae sp. (e.g., cucumbers), Alliaceae sp. (e.g., leeks, onions), Papilionaceae sp. (e.g., peas); major crop plants, such as Gramineae sp. (e.g., corn, turfgrass, cereals (such as wheat, rye, rice, barley, oats, millet, and triticale)), Asteraceae sp. (e.g., sunflowers), Brassicaceae sp. (e.g., white cabbage, red cabbage, kohlrabi, cauliflower, Brussels sprouts, pak choi, turnips, radishes, and also rape, mustard, horseradish, and cress), Fabacae sp. (e.g., kidney beans, peanuts), Papilionaceae sp. (e.g., soybeans), Solanaceae sp. (e.g., potatoes), Chenopodiaceae sp.)(e.g., sugar beet, fodder beet, Swiss chard, beetroot); useful and ornamental plants in gardens and forests; and genetically modified varieties of these plants respectively.

[0521] In some preferred embodiments, wild plant species and plant cultivars or those plants and their parts obtained by conventional biobreeding methods (e.g., crossing or protoplast fusion) are treated according to the present invention.

[0522] In some other preferred embodiments, transgenic plants and plant cultivars (genetically modified organisms) and their parts obtained by genetic engineering methods (if appropriate, in combination with conventional methods) are treated according to the method of the present invention. More preferably, plants of commercially available or in-use plant cultivars can be treated according to the present invention. Plant cultivars should be understood to mean plants that have new characteristics ("traits") and have been obtained by conventional breeding methods, mutagenesis or recombinant DNA technology. They can be cultivars, varieties, biotypes or genotypes.

[0523] The treatment method of the present invention can be used to treat genetically modified organisms (GMOs), such as plants or seeds. Genetically modified plants (or transgenic plants) are plants in which a heterologous gene has been stably integrated into the genome. The term "heterologous gene" mainly refers to a gene provided or assembled outside the plant, and when this gene is introduced into the nuclear, chloroplast or mitochondrial genome, it confers new or improved agronomic characteristics or other characteristics to the transformed plant by expressing the protein or polypeptide of interest or by downregulating or silencing one or more other genes present in the plant (e.g., using antisense technology, co-suppression technology or RNA interference - [RNAi] - technology or microRNA - miRNA - technology). A heterologous gene located within the genome is also called a transgene. A transgene defined according to its specific position within the plant genome is called a transformant line or transgenic line.

[0524] Plants and plant cultivars treated according to the methods disclosed above include all plants (whether obtained by breeding and / or biotechnological methods) having genetic material that confers particularly advantageous useful traits to these plants.

[0525] Plants and plant cultivars that can be treated by the methods disclosed above include plants and plant cultivars that are resistant to one or more biotic stresses, i.e., the plants have better defenses against animal and microbial pests (e.g., nematodes, insects, mites, plant pathogenic fungi, bacteria, viruses and / or viroids).

[0526] Plants and plant cultivars that can be treated by the methods disclosed above include those that are resistant to one or more abiotic stresses. Abiotic stress conditions can include, for example, drought, cold exposure, heat exposure, osmotic stress, waterlogging, increased soil salinity, enhanced mineral exposure, ozone exposure, high light exposure, limited nitrogen nutrient availability, limited phosphorus nutrient availability, and shade avoidance.

[0527] Plants and plant cultivars that can be treated by the methods disclosed above include those that are characterized by improved yield characteristics. The improved yield in such plants can be the result of, for example, improved plant physiology, growth, and development, such as water use efficiency, water holding efficiency, improved nitrogen utilization, enhanced carbon assimilation, improved photosynthesis, increased germination rate, and accelerated maturation. Yield can also be affected by an improved plant architecture (under both stress and non-stress conditions), which includes, but is not limited to, earlier flowering, flowering control for hybrid seed production, seedling vigor, plant size, number and spacing of internodes, root growth, seed size, fruit size, pod size, number of pods or ears, number of seeds per pod or ear, seed quality, enhanced seed plumpness, reduced seed dispersal, reduced pod shattering, and lodging resistance. Other yield traits include seed composition, such as carbohydrate content and composition, e.g., cotton or starch, protein content, oil content and composition, nutritional value, reduction of anti-nutritional compounds, improved processability, and better storage stability.

[0528] Plants and plant cultivars that can be treated by the methods disclosed above include plants and plant cultivars that are hybrid plants, which have exhibited characteristics of heterosis or hybrid vigor, which generally results in higher yields, vigor, health, and resistance to biotic and abiotic stresses.

[0529] Plants and plant cultivars that can be treated by the methods disclosed above (obtained by plant biotechnology methods such as genetic engineering) include plants or plant cultivars that are herbicide-tolerant plants, i.e., plants that are tolerant to one or more given herbicides. Such plants can be obtained by genetic transformation or by selecting plants that contain mutations conferring such herbicide tolerance.

[0530] Plants and plant cultivars that can be treated by the methods disclosed above (obtained by plant biotechnology methods such as genetic engineering) include plants or plant cultivars that are insect-resistant transgenic plants, i.e., plants that are resistant to the infestation of certain target insects. Such plants can be obtained by genetic transformation or by selecting plants that contain mutations conferring such insect resistance.

[0531] Plants and plant cultivars (obtained by plant biotechnology methods such as genetic engineering) that can be treated by the methods disclosed above include plants and plant cultivars that are tolerant to abiotic stresses. Such plants can be obtained by genetic transformation or by selecting plants that contain mutations conferring resistance to such stresses.

[0532] Plants and plant cultivars (obtained by plant biotechnology methods such as genetic engineering) that can be treated by the methods disclosed above include such plants or plant cultivars that exhibit altered quantity, quality, and / or storage stability of the harvested product, and / or altered properties of specific components of the harvested product.

[0533] Plants and plant cultivars (obtained by plant biotechnology methods such as genetic engineering) that can be treated by the methods disclosed above include plants and plant cultivars having altered fiber properties, such as cotton plants. Such plants can be obtained by genetic transformation or by selecting plants that contain mutations conferring such altered fiber properties.

[0534] Plants and plant cultivars (obtained by plant biotechnology methods such as genetic engineering) that can be treated by the methods disclosed above include plants and plant cultivars having altered oil distribution properties, such as oilseed rape or related Brassica plants. Such plants can be obtained by genetic transformation or by selecting plants that contain mutations conferring such altered oil distribution properties.

[0535] Plants and plant cultivars (obtained by plant biotechnology methods such as genetic engineering) that can be treated by the methods disclosed above include plants and plant cultivars having altered seed shattering properties, such as oilseed rape or related Brassica plants. Such plants can be obtained by genetic transformation or by selecting plants that contain mutations conferring such altered seed shattering characteristics, and include plants having delayed or reduced seed shattering, such as oilseed rape plants.

[0536] Plants and plant cultivars (obtained by plant biotechnology methods such as genetic engineering) that can be treated by the methods disclosed above include plants and plant cultivars having an altered pattern of post-translational protein modification, such as tobacco plants.

[0537] Pathogens and diseases

[0538] The methods disclosed above can be used to control microorganisms, in particular phytopathogenic microorganisms causing diseases, such as phytopathogenic fungi, such as:

[0539] Diseases caused by powdery mildew pathogens, such as pathogens of the genus Blumeria (e.g., Blumeria graminis), Podosphaera (e.g., Podosphaera leucotricha), Sphaerotheca (e.g., Sphaerotheca fuliginea), Uncinula (e.g., Uncinula necator);

[0540] Diseases caused by rust pathogens, such as pathogens of the genus Gymnosporangium (e.g., Gymnosporangium sabinae); Hemileia (e.g., Hemileia vastatrix); Phakopsora (e.g., Phakopsora pachyrhizi and Phakopsora meibomiae); Puccinia (e.g., Puccinia recondite, P. triticina, P. graminis or P. striiformis); Uromyces (e.g., Uromyces appendiculatus);

[0541] Diseases caused by Oomycetes pathogens, such as those of the genus Albugo (e.g., Albugo candida); Bremia (e.g., Bremia lactucae); Peronospora (e.g., Peronospora pisi or Peronospora brassicae); Phytophthora (e.g., Phytophthora infestans); Plasmopara (e.g., Plasmopara viticola); Pseudoperonospora (e.g., Pseudoperonospora humuli or Pseudoperonospora cubensis); Pythium (e.g., Pythium ultimum).

[0542] Leaf spot blight and leaf wilt diseases caused by the following pathogens: for example, species of the genus Alternaria (e.g., Alternaria solani); species of the genus Cercospora (e.g., Cercospora beticola); species of the genus Cladiosporium (e.g., Cladiosporium cucumerinum); species of the genus Cochliobolus (e.g., Cochliobolus sativus (conidial form: Drechslera, synonym: Helminthosporium), Cochliobolus miyabeanus); species of the genus Colletotrichum (e.g., Colletotrichum lindemuthanium); species of the genus Cycloconium (e.g., Cycloconium oleaginum); species of the genus Diaporthe (e.g., Diaporthe citri); species of the genus Elsinoe (e.g., Elsinoe fawcettii); species of the genus Gloeosporium (e.g., Gloeosporium laeticolor); species of the genus Glomerella (e.g., Glomerella cingulata); species of the genus Guignardia (e.g., Guignardia bidwelli); species of the genus Leptosphaeria (e.g., Leptosphaeria maculans); species of the genus Magnaporthe (e.g., Magnaporthe grisea); species of the genus Microdochium (e.g., Microdochium nivale); species of the genus Mycosphaerella (e.g., Mycosphaerella graminicola, Mycosphaerella arachidicola, and Mycosphaerella fijiensis);Species of the genus Phaeosphaeria (such as Phaeosphaeria nodorum); species of the genus Pyrenophora (such as Pyrenophora teres, Pyrenophora tritici repentis); species of the genus Ramularia (such as Ramularia collo-cygni or Ramularia areola); species of the genus Rhynchosporium (such as Rhynchosporium secalis); species of the genus Septoria (such as Septoria apii or Septoria lycopersii); species of the genus Stagonospora (such as Stagonospora nodorum); species of the genus Typhula (such as Typhula incarnata); species of the genus Venturia (such as Venturia inaequalis);

[0543] Root and stem diseases caused by the following pathogens: for example, species of the genus Corticium (such as Corticium graminearum); species of the genus Fusarium (such as Fusarium oxysporum); species of the genus Gaeumannomyces (such as Gaeumannomyces graminis); species of the genus Plasmodiophora (such as Plasmodiophora brassicae); species of the genus Rhizoctonia (such as Rhizoctonia solani); diseases of the genus Sarocladium caused by, for example, Sarocladium oryzae; diseases of the genus Sclerotium caused by, for example, Sclerotium oryzae; species of Tapesia (such as Tapesia acuformis); species of the genus Thielaviopsis (such as Thielaviopsis basicola);

[0544] Spathe and panicle diseases (including maize cobs) caused by the following pathogens: for example, species of Alternaria (e.g., Alternaria spp.); species of Aspergillus (e.g., Aspergillus flavus); species of Cladosporium (e.g., Cladosporium cladosporioides); species of Claviceps (e.g., Claviceps purpurea); species of Fusarium (e.g., Fusarium culmorum); species of Gibberella (e.g., Gibberella zeae); species of Monographella (e.g., Monographella nivalis); species of Stagnospora (e.g., Stagnospora nodorum);

[0545] Diseases caused by smut fungi, said pathogens being for example: species of Sphacelotheca (e.g., Sphacelotheca reiliana); species of Tilletia (e.g., Tilletia caries or Tilletia controversa); species of Urocystis (e.g., Urocystis occulta); species of Ustilago (e.g., Ustilago nuda);

[0546] Fruit rot diseases caused by the following pathogens: for example, species of the genus Aspergillus (such as Aspergillus flavus); species of the genus Botrytis (such as Botrytis cinerea); species of the genus Penicillium (such as Penicillium expansum and Penicillium purpurogenum); species of the genus Rhizopus (such as Rhizopus stolonifer); species of the genus Sclerotinia (such as Sclerotinia sclerotiorum); species of the genus Verticilium (such as Verticilium alboatrum);

[0547] Seed-borne and soil-borne rot and wilt diseases, as well as seedling diseases, caused by the following pathogens: for example, species of the genus Alternaria (e.g., Alternaria brassicicola); species of the genus Aphanomyces (e.g., Aphanomyces euteiches); species of the genus Ascochyta (e.g., Ascochyta lentis); species of the genus Aspergillus (e.g., Aspergillus flavus); species of the genus Cladosporium (e.g., Cladosporium herbarum); species of the genus Cochliobolus (e.g., Cochliobolus sativus (conidial form: Drechslera, synonym of Bipolaris: Helminthosporium)); species of the genus Colletotrichum (e.g., Colletotrichum coccodes); species of the genus Fusarium (e.g., Fusarium culmorum); species of the genus Gibberella (e.g., Gibberella zeae); species of the genus Macrophomina (e.g., Macrophomina phaseolina); species of the genus Microdochium (e.g., Microdochium nivale); species of the genus Monographella (e.g., Monographella nivalis); species of the genus Penicillium (e.g., Penicillium expansum); species of the genus Phoma (e.g., Phoma lingam); species of the genus Phomopsis (e.g., Phomopsis sojae); species of the genus Phytophthora (e.g., Phytophthora cactorum); species of the genus Pyrenophora (e.g., Pyrenophora graminea); species of the genus Pyricularia (e.g., Pyricularia oryzae);Species of the genus Pythium (e.g., Pythium ultimum); species of the genus Rhizoctonia (e.g., Rhizoctonia solani); species of the genus Rhizopus (e.g., Rhizopus oryzae); species of the genus Sclerotium (e.g., Sclerotium rolfsii); species of the genus Septoria (e.g., Septoria nodorum); species of the genus Typhula (e.g., Typhula incarnata); species of the genus Verticillium (e.g., Verticillium dahliae);

[0548] Cancerous diseases, galls, and witches' brooms caused by the following pathogens: for example, species of the genus Nectria (e.g., Nectria galligena);

[0549] Wilt diseases caused by the following pathogens: for example, species of the genus Monilinia (e.g., Monilinia laxa);

[0550] Deformations of leaves, flowers, and fruits caused by the following pathogens: for example, the genus Exobasidium (e.g., Exobasidium vexans); the genus Taphrina (e.g., Taphrina deformans);

[0551] Degenerative diseases of woody plants caused by the following pathogens: for example, species of the genus Esca (e.g., Phaeomoniella clamydospora, Phaeoacremonium aleophilum, and Fomitiporia mediterranea); species of the genus Ganoderma (e.g., Ganoderma boninense);

[0552] Diseases of flowers and seeds caused by the following pathogens: for example, species of the genus Botrytis (e.g., Botrytis cinerea);

[0553] Plant tuber diseases caused by the following pathogens: for example, species of the genus Rhizoctonia (e.g., Rhizoctonia solani); species of the genus Helminthosporium (e.g., Helminthosporium solani).

[0554] Diseases caused by the following bacterial pathogens: for example, species of the genus Xanthomonas (e.g., Xanthomonas campestris pv. oryzae); species of the genus Pseudomonas (e.g., Pseudomonas syringae pv. lachrymans); species of the genus Erwinia (e.g., Erwinia amylovora).

[0555] Seed treatment

[0556] Methods for controlling unwanted microorganisms can be used to protect seeds from plant pathogenic microorganisms such as fungi.

[0557] As used herein, the term "seed" includes dormant seeds, pretreated seeds, pre-germinated seeds, and seeds with emerged roots and leaves.

[0558] Accordingly, the present invention also relates to a method for protecting seeds and / or crops from unwanted microorganisms such as bacteria or fungi, which comprises the step of treating the seeds with one or more compounds of formula (I) or formula (II) or a composition comprising the same. Treating the seeds with one or more compounds of formula (I) or formula (II) or a composition comprising the same not only protects the seeds from plant pathogenic microorganisms, but also protects the germinated plants, emerged seedlings, and plants after emergence.

[0559] Seed treatment can be carried out before sowing, at sowing, or shortly after sowing.

[0560] When seed treatment is carried out before sowing (e.g., so-called application on the seeds), the seed treatment can be carried out as follows: the seeds can be placed in a mixer containing the required amount of the compound of formula (I) or formula (II) or a composition containing the same (as such or diluted), and the seeds and the compound of formula (I) or formula (II) or a composition containing the same are mixed until evenly distributed on the seeds. If appropriate, the seeds can then be dried.

[0561] The present invention also relates to seeds treated with a compound of formula (I) or (II) or a composition comprising the same. As described above, the use of treated seeds can not only protect the seeds from unwanted microorganisms (such as phytopathogenic fungi) before and after sowing, but also protect the germinated plants and seedlings grown from the treated seeds. Most of the damage caused by pests to crop plants is triggered by the infection of seeds before sowing or after plant germination. This stage is particularly critical because the roots and buds of the growing plants are particularly sensitive, and even minor damage can lead to plant death.

[0562] Accordingly, the present invention also relates to a method for protecting seeds, germinated plants and emerged seedlings, and more generally to a method for protecting crops from phytopathogenic microorganisms, which comprises the step of treating seeds with a compound of formula (I) or (II) or a composition comprising the same.

[0563] Preferably, the seeds are treated in a state where they are stable enough not to be damaged during the treatment process. Generally, the seeds can be treated at any time between harvest and just after sowing. Seeds that have been separated from plants and have had their cores, husks, stems, skins, fuzz or pulp removed are usually used. For example, seeds that have been harvested, cleaned and dried to a water content of less than 15% by weight can be used. Alternatively, seeds that have been dried and then treated with water and dried again, or only pre-treated seeds, or seeds stored under pre-treatment conditions or pre-germinated seeds, or seeds planted in nursery trays, strips or on paper can also be used.

[0564] The amount of the compound of formula (I) or (II) or the composition comprising the same applied to the seeds generally does not damage the germination of the seeds or the grown plants. This must be ensured especially in the case of active ingredients that may exhibit phytotoxic effects at certain application rates. The inherent phenotype of transgenic plants should also be considered when determining the amount of the compound of formula (I) or (II) or the composition comprising the same applied to the seeds, so as to achieve the best protection of the seeds and germinated plants with the least amount of the compound of formula (I) or (II) or the composition comprising the same.

[0565] As described above, the compounds of formula (I) or (II) can be applied directly to the seeds, i.e., without using any other components and without dilution, or a composition comprising the compound of formula (I) or (II) can be applied. Preferably, the composition is applied to the seeds in any suitable form. Examples of suitable formulations include solutions, emulsions, suspensions, powders, foams, slurries or in combination with other coating compositions for seeds, such as film-forming materials, pelleting materials, fine iron powder or other metal powders, granules, coating materials for inactivating seeds, and ULV formulations. The formulations can be ready-to-use formulations or concentrates that need to be diluted before use.

[0566] These formulations are prepared in a known manner, for example by mixing the active ingredient or its mixture with conventional additives, which are, for example, conventional extenders and solvents or diluents, dyes, wetting agents, dispersants, emulsifiers, defoamers, preservatives, secondary thickeners, adhesives, gibberellins and water.

[0567] These formulations are prepared in a known manner by mixing the active ingredient or active ingredient combination with conventional additives, which are, for example, conventional extenders and solvents or diluents, dyes, wetting agents, dispersants, emulsifiers, defoamers, preservatives, secondary thickeners, adhesives, gibberellins and water.

[0568] Useful dyes that can be present in the seed dressing preparation are all dyes commonly used for this purpose. Pigments slightly soluble in water or dyes soluble in water can be used. Examples include the dyes known by the names rhodamine B, C.I. Pigment Red 112, and C.I. Solvent Red 1. Useful wetting agents that can be present in the seed dressing preparation are all substances that promote wetting and are commonly used in preparations of active agrochemical ingredients. Alkyl naphthalenesulfonates, such as diisopropyl naphthalenesulfonate or diisobutyl naphthalenesulfonate, are preferably used. Useful dispersants and / or emulsifiers that can be present in the seed dressing preparation are all nonionic, anionic, and cationic dispersants commonly used in preparations of active agrochemical ingredients. Nonionic or anionic dispersants or mixtures of nonionic or anionic dispersants can be preferably used. Suitable nonionic dispersants particularly include ethylene oxide / propylene oxide block polymers, alkylphenol polyethylene glycol ethers, and triphenylvinylphenol polyethylene glycol ethers, as well as their phosphorylated or sulfated derivatives. Suitable anionic dispersants are particularly lignosulfonates, polyacrylates, and arylsulfonates / formaldehyde condensates. Defoaming agents that can be present in the seed dressing preparation are all foam-inhibiting substances commonly used in preparations of active agrochemical ingredients. Silicone defoaming agents and magnesium stearate can be preferably used. Preservatives that can be present in the seed dressing preparation are all substances that can be used for this purpose in agrochemical compositions. Examples include dichlorophen and benzyl alcohol hemiacetal. Secondary thickeners that can be present in the seed dressing preparation are all substances that can be used for this purpose in agrochemical compositions. Preferred examples include cellulose derivatives, acrylic derivatives, xanthan gum, modified clays, and finely divided silica. Adhesives that can be present in the seed dressing preparation are all conventional binders that can be used for seed dressing products. Preferred examples include polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol, and methylcellulose.

[0569] Compounds of formula (I) or formula (II) and compositions containing them are suitable for protecting the seeds of any plant variety used in agriculture, in greenhouses, in forests, or in horticulture. More specifically, the seeds are cereals (such as wheat, barley, rye, millet, triticale, and oats), rapeseed, corn, cotton, soybeans, rice, potatoes, sunflowers, legumes, coffee, peas, beets (such as sugar beets and fodder beets), peanuts, vegetables (such as tomatoes, cucumbers, onions, and lettuce), lawns, and ornamental plants. The treatment of wheat, soybean, rapeseed, corn, and rice seeds is particularly important.

[0570] Compounds of formula (I) or formula (II) or compositions containing them can be used to treat genetically modified seeds, particularly plant seeds capable of expressing proteins against pests, herbicidal damage, or abiotic stress, thereby increasing the protective effect. Synergistic effects may also occur in the interaction with the substances formed by the expression.

[0571] Nematodes

[0572] In the present text, the term "nematode" includes all species of the phylum Nematoda and, in particular, those species which act as parasites on plants or fungi (e.g., species of the order Aphelenchida, genus Meloidogyne, order Tylenchida, etc.) or on humans and animals (e.g., species of the order Trichinellida, Tylenchida, Rhabditida and Spirurida) and which cause damage in or on these living organisms, as well as other parasitic worms.

[0573] As described herein, nematicides in crop protection are capable of controlling nematodes.

[0574] The term "controlling nematodes" means killing nematodes or preventing or inhibiting their development or their growth or preventing or inhibiting their penetration or feeding on plant tissue.

[0575] In the present text, the efficacy of a compound is determined as follows: by comparing the nematode mortality, gall formation, cyst formation, nematode density per volume of soil, nematode density per root, number of nematode eggs per volume of soil, nematode motility between plants or plant parts treated with a compound of formula (I) or treated soil and untreated plants or plant parts or untreated soil (100%). Preferably, the reduction achieved is 25 - 50% compared to untreated plants, plant parts or untreated soil, particularly preferably 51 - 79%, and very particularly preferably complete killing of nematodes or complete prevention of nematode development and growth by achieving a reduction of 80% to 100%. Controlling nematodes as described herein also includes controlling nematode reproduction (development of cysts and / or eggs). Compounds of formula (I) or (II) can also be used to maintain the health of plants or animals and they can be used therapeutically, prophylactically or systemically to control nematodes.

[0576] Those skilled in the art are aware of methods for determining nematode mortality, gall formation, cyst formation, nematode density per volume of soil, nematode density per root, number of nematode eggs per volume of soil, nematode motility.

[0577] Using a compound of formula (I) or (II) can maintain the health of plants and also includes reducing damage caused by nematodes and increasing the harvest yield.

[0578] As used herein, the term "nematode" refers to plant nematodes, which include all nematodes that damage plants. Plant nematodes include plant parasitic nematodes and soil-borne nematodes. Plant parasitic nematodes include ectoparasites such as Xiphinema spp., Longidorus spp., and Trichodorus spp.; semi-parasites such as Tylenchulus spp.; migratory endoparasites such as Pratylenchus spp., Radopholus spp., and Scutellonema spp.; non-migratory parasites such as Heterodera spp., Globodera spp., and Meloidogyne spp.; and stem and leaf endoparasites such as Ditylenchus spp., Aphelenchoides spp., and Hirshmaniella spp. Particularly harmful root-parasitic soil nematodes are, for example, cyst-forming nematodes of the genus Heterodera or Globodera, and / or root-knot nematodes of the genus Meloidogyne. Harmful species of these genera are, for example, Meloidogyne incognita, Heterodera glycines (soybean cyst nematode), Globodera pallida, and Globodera rostochiensis (yellow potato cyst nematode), and these species can be effectively controlled by the compounds described herein. However, the use of the compounds described herein is in no way limited to these genera or species, but extends in the same manner to other nematodes.

[0579] Plant nematodes include, for example, Aglenchus agricola; Anguina tritici; Aphelenchoides arachidis, Aphelenchoides fragaria, and parasites in the stems and leaves of Aphelenchoides spp.; Belonolaimus gracilis, Belonolaimus longicaudatus, Belonolaimus nortoni, Bursaphelenchus cocophilus, Bursaphelenchus eremus, Bursaphelenchus xylophilus, and Bursaphelenchus spp.; Cacopaurus pestis; Criconemella curvata, Criconemella onoensis, Criconemella ornata, Criconemella rusium, Criconemella xenoplax (= Mesocriconemaxenoplax), and Criconemella spp.; Criconemoides ferniae, Criconemoides onoense, Criconemoides ornatum, and Criconemoides spp.; Ditylenchus destructor, Ditylenchus dipsaci, Ditylenchus myceliophagus, and Ditylenchus spp.) parasites in the stems and leaves; Dolichodorus heterocephalus, potato white nematode (Globodera pallida) ( = Heterodera pallida), potato golden nematode (Globodera rostochiensis) (potato cyst nematode), Globodera solanacearum, Globodera tabacum, Globodera virginia and non-migratory cyst-forming parasites of the genus Globodera; Helicotylenchus digonicus, Helicotylenchus dihystera, Helicotylenchus erythrine, Helicotylenchus multicinctus, Helicotylenchus nannus, Helicotylenchus pseudorobustus and the genus Helicotylenchus; the genus Hemicriconemoides; Hemicycliophora arenaria, Hemicycliophora nudata, Hemicycliophora parvana; Heterodera avenae, Heterodera cruciferae, Heterodera glycines (soybean cyst nematode), Heterodera oryzae, Heterodera schachtii, Heterodera zeae and non-migratory cyst-forming parasites of the genus Heterodera; Hirschmaniella gracilis, Hirschmaniella oryzae, Hirschmaniella spinicaudata and the genus HirschmaniellaStem and leaf parasites of (), Hoplolaimus aegyptii, Hoplolaimus californicus, Hoplolaimus columbus, Hoplolaimus galeatus, Hoplolaimus indicus, Hoplolaimus magnistylus, Hoplolaimus pararobustus; Longidorus africanus, Longidorus breviannulatus, Longidorus elongatus, Longidorus laevicapitatus, Longidorus vineacola, and Longidorus spp.) ectoparasites; sedentary endoparasites of Meloidogyne acronea, Meloidogyne africana, Meloidogyne arenaria, Meloidogyne arenaria thamesi, Meloidogyne artiella, Meloidogyne chitwoodi, Meloidogyne coffeicola, Meloidogyne ethiopica, Meloidogyne exigua, Meloidogyne fallax, Meloidogyne graminicola, Meloidogyne graminis, Meloidogyne hapla, Meloidogyne incognita, Meloidogyne incognita acrita, Meloidogyne javanica, Meloidogyne kikuyensis, Meloidogyne minor, Meloidogyne naasi, Meloidogyne paranaensis, Meloidogyne thamesi and Meloidogyne spp.; Meloinema spp.; Nacobbus aberrans; Neotylenchus vigissi; Paraphelenchus pseudoparietinus; Paratrichodorus allius, Paratrichodorus lobatus, Paratrichodorus minor, Paratrichodorus nanus, Paratrichodorus porosus, Paratrichodorus teres and Paratrichodorus spp.), migratory endoparasites of Paratylenchus hamatus, Paratylenchus minutus, Paratylenchus projectus, and Paratylenchus spp.; Pratylenchus agilis, Pratylenchus alleni, Pratylenchus andinus, Pratylenchus brachyurus, Pratylenchus cerealis, Pratylenchus coffeae, Pratylenchus crenatus, Pratylenchus delattrei, Pratylenchus giibbicaudatus, Pratylenchus goodeyi, Pratylenchus hamatus, Pratylenchus hexincisus, Pratylenchus loosi, Pratylenchus neglectus, Pratylenchus penetrans, Pratylenchus pratensis, Pratylenchus scribneri, Pratylenchus teres, Pratylenchus thornei, Pratylenchus vulnus, Pratylenchus zeae, and Pratylenchus spp.; Pseudohalenchus minutus; Psilenchus magnidens, Psilenchus tumidus; Punctodera chalcoensis; Quinisulcius acutus; Radopholus citrophilus, Radopholus similis, and Radopholus spp.) migratory endoparasites of Rotylenchulus borealis, Rotylenchulus parvus, Rotylenchulus reniformis, and Rotylenchulus spp.; Rotylenchus laurentinus, Rotylenchus macrodoratus, Rotylenchus robustus, Rotylenchus uniformis, and Rotylenchus spp.; migratory endoparasites of Scutellonema brachyurum, Scutellonema bradys, Scutellonema clathricaudatum, and Scutellonema spp.; Subanguina radiciola, Tetylenchus nicotianae; ectoparasites of Trichodorus cylindricus, Trichodorus minor, Trichodorus primitivus, Trichodorus proximus, Trichodorus similis, Trichodorus sparsus, and Trichodorus spp.; Tylenchorhynchus agri, Tylenchorhynchus brassicae, Tylenchorhynchus clarus, Tylenchorhynchus claytoni, Tylenchorhynchus digitatus, Tylenchorhynchus ebriensis, Tylenchorhynchus maximus, Tylenchorhynchus nudus, Tylenchorhynchus vulgaris, and Tylenchorhynchus spp.);Semiparasites of Tylenchulus semipenetrans and Tylenchulus spp.; Ectoparasites of Xiphinema americanum, Xiphinema brevicolle, Xiphinema dimorphicaudatum, Xiphinema index and Xiphinema spp..

[0580] Nematodes that can be controlled using the compounds of formula (I) or formula (II) include: nematodes of the genus Meloidogyne, such as Meloidogyne incognita, Meloidogyne javanica, Meloidogyne hapla, and Meloidogyne arenaria; nematodes of the genus Ditylenchus, such as Ditylenchus destructor (potato rot nematode) and Ditylenchus dipsaci (stem and bulb nematode); nematodes of the genus Pratylenchus, such as Pratylenchus penetrans (corn root lesion nematode), Pratylenchus fallax (chrysanthemum root lesion nematode), Pratylenchus coffeae (coffee root lesion nematode), Pratylenchus loosi (tea tree root lesion nematode), and Pratylenchus vulnus (walnut root lesion nematode); nematodes of the genus Globodera, such as Globodera rostochiensis (golden potato cyst nematode) and Globodera pallida (white potato cyst nematode); nematodes of the genus Heterodera, such as Heterodera glycines (soybean cyst nematode) and Heterodera schachtii (beet cyst nematode); nematodes of the genus Aphelenchoides, such as Aphelenchoides besseyi (rice white tip nematode), Aphelenchoides ritzemabosi (chrysanthemum leaf nematode), and Aphelenchoides fragariae (strawberry nematode); nematodes of the genus Aphelenchus, such as Aphelenchus avenae (fungus-feeding nematode); nematodes of the genus Radopholus, such as Radopholus similis (burrowing nematode); nematodes of the genus Tylenchulus, such as Tylenchulus semipenetrans (citrus root nematode);Nematodes of the genus Rotylenchulus, such as Rotylenchulus reniformis; nematodes present in trees, such as Bursaphelenchus xylophilus and Bursaphelenchus cocophilus, etc.

[0581] Plants that can be protected using the compounds of formula (I) or formula (II) include the following plants: for example, cereals (e.g., rice, barley, wheat, rye, oats, corn, etc.), legumes (soybean, adzuki bean, kidney bean, broad bean, pea, peanut, etc.), fruit trees / fruits (apple, citrus, pear, grape, peach, Japanese apricot, cherry, walnut, almond, banana, strawberry, etc.), vegetables (cabbage, tomato, spinach, cauliflower, lettuce, onion, scallion, pepper, etc.), root crops (carrot, potato, sweet potato, radish, lotus root, turnip, etc.), industrial raw material plants (cotton, hemp, Broussonetia papyrifera, Wikstroemia japonica, rape, sugar beet, hops, sugarcane, sugar beet, olive, rubber, palm tree, coffee, tobacco, tea, etc.), melons (pumpkin, cucumber, watermelon, muskmelon, etc.), forage plants (cocksfoot, sorghum, timothy grass, clover, alfalfa, etc.), lawn grasses (Zoysia japonica, Agrostis stolonifera, etc.), spice plants (lavender, rosemary, thyme, parsley, pepper, ginger, etc.), etc., and flowers (chrysanthemum, rose, orchid, etc.).

[0582] The compounds of formula (I) or formula (II) are particularly suitable for controlling coffee nematodes, especially Pratylenchus brachyurus, Pratylenchus coffeae, Meloidogyne exigua, Meloidogyne incognita, Meloidogyne coffeicola, Helicotylenchus spp., as well as Meloidogyne paranaensis, Rotylenchus spp., Xiphinema spp., Tylenchorhynchus spp., and Scutellonema spp.

[0583] Compounds of formula (I) or formula (II) are particularly suitable for controlling potato nematodes, especially Pratylenchus brachyurus, Pratylenchus pratensis, Pratylenchus scribneri, Pratylenchus penetrans, Pratylenchus coffeae, Ditylenchus dipsaci, as well as Pratylenchus alleni, Pratylenchus andinus, Pratylenchus cerealium, Pratylenchus sculptus, Pratylenchus hexincisus, Pratylenchus loosi, Pratylenchus neglectus, Pratylenchus laevis, Pratylenchus thornei, Pratylenchus vulnus, Trichodorus caudatus, Trichodorus cylindricus, Trichodorus primitivus, Trichodorus proximus, Trichodorus similis, Trichodorus rarus, Paratrichodorus minor, Paratrichodorus allii, Paratrichodorus brevicaudatus, Paratrichodorus laevis, Meloidogyne arenaria, Meloidogyne fallax, Meloidogyne hapla, Meloidogyne thamesiensis, Meloidogyne incognita, Meloidogyne chitwoodi, Meloidogyne javanica, Nacobbus aberrans, Globodera rostochiensis, Globodera pallida, Ditylenchus destructor, Radopholus similis, Rotylenchulus reniformis, Neotylenchus vigissi, Aphelenchoides pseudococci, Aphelenchoides fragariae, and species of Meloinema.

[0584] Compounds of formula (I) or formula (II) are particularly suitable for controlling tomato nematodes, especially Meloidogyne arenaria, Meloidogyne hapla, Meloidogyne javanica, Meloidogyne incognita, Pratylenchus penetrans, as well as Pratylenchus brachyurus, Pratylenchus coffeae, Pratylenchus scribneri, Pratylenchus vulnus, Paratrichodorus minor, Pratylenchus brachyurus, Nacobbus aberrans, Globodera tabacum, Dolichodorus heterocephalus, and Rotylenchulus reniformis.

[0585] Compounds of formula (I) or formula (II) are particularly suitable for controlling nematodes in cucumber plants, especially Meloidogyne arenaria, Meloidogyne hapla, Meloidogyne javanica, Meloidogyne incognita, Rotylenchulus reniformis, and Pratylenchus thornei.

[0586] Compounds of formula (I) or formula (II) are particularly suitable for controlling cotton nematodes, especially Trichodorus caudatus, Meloidogyne incognita, Hoplolaimus columbus, Hoplolaimus galeatus, and Rotylenchulus reniformis.

[0587] Compounds of formula (I) or formula (II) are particularly suitable for controlling nematodes in maize, especially Belonolaimus longicaudatus, Paratrichodorus minor, Pratylenchus brachyurus, Pratylenchus delattrei, Pratylenchus hexincisus, Pratylenchus penetrans, Pratylenchus zeae, (Belonolaimus gracilis), Belonolaimus nortoni, Longidorus breviannulatus, Meloidogyne arenaria, Meloidogyne arenaria thamesi, Meloidogyne graminicola, Meloidogyne incognita, Meloidogyne incognita acrita, Meloidogyne javanica, Meloidogyne naasi, Heterodera avenae, Heterodera oryzae, Heterodera zeae, Punctodera chalcoensis, Ditylenchus dipsaci, Hoplolaimus aegyptiacus, Hoplolaimus magnicaudatus, Hoplolaimus galeatus, Hoplolaimus indicus, Helicotylenchus dihystera, Helicotylenchus digonicus, Helicotylenchus pseudorobustus, Xiphinema americanum, Dolichodorus heterocephalus, Criconemella ornata, Criconemella onohime, Radopholus similis, Rotylenchulus reniformis, Rotylenchulus parvus, Tylenchorhynchus agri, Tylenchorhynchus clarus, Tylenchorhynchus claytoni, Tylenchorhynchus maximus, Tylenchorhynchus nudus, Tylenchorhynchus vulgaris, Penthaleus sharpianus, Microlaimus sp., Hemicycliophora arenaria, Anguina tritici, Aphelenchoides arachidis, Scutellonema brachyurus, and Subanguina radicicola.

[0588] Compounds of formula (I) or formula (II) are particularly suitable for controlling nematodes in soybean, especially Pratylenchus brachyurus, Pratylenchus pratensis, Pratylenchus penetrans, Pratylenchus scribneri, Belonolaimus longicaudatus, Heterodera glycines, Hoplolaimus columbus, and Pratylenchus coffeae, Pratylenchus hexincisus, Pratylenchus neglectus, Pratylenchus punctatus, Pratylenchus alleni, Pratylenchus agilis, Pratylenchus zeae, Pratylenchus vulnus, (Belonolaimus gracilis), Meloidogyne arenaria, Meloidogyne incognita, Meloidogyne javanica, Meloidogyne hapla, Hoplolaimus columbus, Hoplolaimus galeatus, and Rotylenchulus reniformis.

[0589] Compounds of formula (I) or formula (II) are particularly suitable for controlling nematodes in tobacco, especially Meloidogyne incognita, Meloidogyne javanica, and Pratylenchus brachyurus, Pratylenchus pratensis, Pratylenchus hexincisus, Pratylenchus penetrans, Pratylenchus neglectus, Pratylenchus punctatus, Pratylenchus thornei, Pratylenchus vulnus, Pratylenchus zeae, Longidorus eludens, Paratrichodorus lobatus, Trichodorus spp., Meloidogyne arenaria, Meloidogyne hapla, Globodera tabacum, Globodera solanacearum, Globodera virginiae, Ditylenchus dipsaci, Rotylenchus spp., Helicotylenchus spp., Xiphinema americanum, Criconemella spp., Rotylenchulus reniformis, Tylenchorhynchus claytoni, Microlaimus spp., and Paratrichodorus minor.

[0590] Compounds of formula (I) or formula (II) are particularly suitable for controlling citrus nematodes, especially Pratylenchus coffeae, as well as Pratylenchus brachyurus, Pratylenchus vulnus, Belonolaimus longicaudatus, Paratrichodorus minor, Paratrichodorus pachydermus, Trichodorus spp., Meloidogyne incognita, Meloidogyne incognita acrita, Meloidogyne javanica, Rotylenchulus reniformis, Xiphinema americanum, Xiphinema brevicolle, Xiphinema index, Criconemella spp., Hemicycliophora spp., Radopholus similis, and Tylenchulus semipenetrans, Hemicriconemoides mangiferae, Hemicycliophora nudata, and Tylenchulus semipenetrans.

[0591] Compounds of formula (I) or formula (II) are particularly suitable for controlling banana nematodes, especially Pratylenchus coffeae, Radopholus similis, and Pratylenchus gibbicaudatus, Pratylenchus loosi, Meloidogyne spp., Helicotylenchus multicinctus, Helicotylenchus dihystera, and Rotylenchulus spp.

[0592] Compounds of formula (I) or formula (II) are particularly suitable for controlling pineapple nematodes, especially Pratylenchus zeae, Pratylenchus pratensis, Pratylenchus brachyurus, Pratylenchus goodeyi, Meloidogyne spp., Rotylenchulus reniformis, as well as Longidorus eludens, Longidorus laevicapitatus, Trichodorus primitivus, Trichodorus minor, Heterodera spp., Ditylenchus myceliophagus, Hemicriconemoides californicus, Hemicriconemoides similis, Hemicriconemoides indicus, Helicotylenchus dihystera, Helicotylenchus brevicaudatus, Helicotylenchus multicinctus, Helicotylenchus erythrinae, Xiphinema dimorphicaudatum, Radopholus similis, Tylenchorhynchus ebriensis, Paratylenchus microdorus, Scutellonema clathricaudatum, Trophurus velatus, Paratrichodorus caudatus, Psilenchus magnidens, Pseudohalenchus minutus, Criconemoides ferniae, Criconemoides onoense, and Criconemoides ornatum.

[0593] Compounds of formula (I) or formula (II) are particularly suitable for controlling grape nematodes, especially Pratylenchus vulnus, Meloidogyne arenaria, Meloidogyne incognita, Meloidogyne javanica, Xiphinema americanum, Xiphinema index, as well as Pratylenchus pratensis, Pratylenchus scribneri, Pratylenchus neglectus, Pratylenchus brachyurus, Pratylenchus thornei, and Tylenchulus semipenetrans.

[0594] Compounds of formula (I) or (II) are particularly suitable for controlling nematodes in tree crops - pome fruits, in particular Pratylenchus penetrans as well as Pratylenchus vulnus, Longidorus eludens, Meloidogyne incognita and Meloidogyne hapla.

[0595] Compounds of formula (I) or (II) are particularly suitable for controlling nematodes in tree crops - stone fruits, in particular Pratylenchus penetrans, Pratylenchus vulnus, Meloidogyne arenaria, Meloidogyne hapla, Meloidogyne javanica, Meloidogyne incognita, Criconemella xenoplax as well as Pratylenchus brachyurus, Pratylenchus coffeae, Pratylenchus scribneri, Pratylenchus zeae, Belonolaimus longicaudatus, Helicotylenchus dihystera, Xiphinema americanum, Criconemella curvata, Tylenchorhynchus claytoni, Paratylenchus hamatus, Longidorus elongatus, Scutellonema brachyurus and Hemicriconemoides californianus.

[0596] Compounds of formula (I) or (II) are particularly suitable for controlling nematodes in tree crops, sugar cane and rice, in particular species of Trichodorus, species of Criconemella as well as species of Pratylenchus, species of Paratrichodorus, species of Meloidogyne, species of Helicotylenchus, species of Tylenchorhynchus, species of Aphelenchoides, species of Heterodera, species of Xiphinema and Cacopaurus pestis.

[0597] Application

[0598] Compounds of formula (I) or (II) can be applied by themselves or, for example, in the form of ready-to-use solutions, emulsions, water-based and oil-based suspensions, powders, wettable powders, pastes, soluble powders, dusts, soluble granules, broadcast granules, suspoemulsion concentrates, natural products impregnated with the compound of formula (I) or (II), synthetic substances impregnated with the compound of formula (I) or (II), fertilizers and microcapsules in polymers.

[0599] Application is carried out in a conventional manner, for example by watering, spraying, atomizing, broadcasting, dusting, foaming, spreading, etc. Compounds of formula (I) or (II) can also be applied by the ultra-low volume method (by drip irrigation system or drenching), applying them into furrows or injecting them into the soil stem or tree trunk. Compounds of formula (I) or (II) can also be applied by wound sealing, painting or other wound dressings.

[0600] The effective and phytocompatible amounts of the compounds of formula (I) or (II) applied to plants, plant parts, fruits, seeds or soil will depend on various factors, such as the compound / composition used, the object being treated (plant, plant part, fruit, seed or soil), the type of treatment (dusting, spraying, seed dressing), the purpose of the treatment (therapeutic and protective), the type of microorganism, the developmental stage of the microorganism, the sensitivity of the microorganism, the crop growth stage and the environmental conditions.

[0601] When the compounds of formula (I) or formula (II) are used as fungicides, the application rates can vary within a wide range depending on the type of application. For the treatment of plant parts such as leaves, the application rate can be from 0.1 to 10,000 g / ha, preferably from 10 to 1000 g / ha, more preferably from 50 to 300 g / ha (in the case of application by watering or drip irrigation, the application rate can even be reduced, especially when using inert materials such as rock wool or perlite). For the treatment of seeds, the application rate can be from 0.1 to 200 g per 100 kg of seeds, preferably from 1 to 150 g per 100 kg of seeds, more preferably from 2.5 to 25 g per 100 kg of seeds, and even more preferably from 2.5 to 12.5 g per 100 kg of seeds. For the treatment of soil, the application rate can be from 0.1 to 10,000 g / ha, preferably from 1 to 5000 g / ha.

[0602] These application rates are merely exemplary and are not intended to limit the scope of the invention.

[0603] Material protection

[0604] The compounds and compositions of the present invention can also be used for the protection of materials, in particular for protecting industrial materials from the attack and destruction by unwanted microorganisms.

[0605] In addition, the compounds of the present invention can be used alone or in combination with other active ingredients as antifouling compositions.

[0606] In the context of this text, industrial materials are understood to mean inanimate materials prepared for use in industry. For example, industrial materials protected from microbial alteration or destruction can be adhesives, glues, paper, wallpaper and wood panels / cardboard, textiles, carpets, leather, wood, fibers and fabrics, paints and plastic products, cooling lubricants and other materials that can be infested or damaged by microorganisms. Also mentioned within the scope of the materials to be protected are components of production equipment and buildings, such as cooling water circuits, cooling and heating systems as well as ventilation units and air conditioning equipment, which can be affected by microbial growth. Within the scope of the present invention, industrial materials preferably include adhesives, sizing agents, paper and cardboard, leather, wood, paints, cooling lubricants and heat transfer fluids, more preferably wood.

[0607] The compounds or compositions of the present invention can prevent adverse effects such as rotting, decay, discoloration, fading or the formation of mildew.

[0608] In the case of treating wood, the compounds and compositions of the present invention can also be used to resist fungal diseases that are prone to grow on or within timber.

[0609] Wood means all types of wood species and all types of processed products of such wood for use in buildings, such as solid wood, high-density wood, laminated wood, and plywood. In addition, the compounds and compositions of the present invention can be used to protect objects (especially ship hulls, sieves, nets, buildings, mooring appliances, and signaling systems) in contact with seawater or brackish water from contamination.

[0610] The compounds and compositions of the present invention can also be used to protect stored goods. Stored goods are understood to mean natural substances of plant or animal origin or processed products of natural origin that require long-term protection. Stored goods of plant origin, such as plants or plant parts, such as stems, leaves, tubers, seeds, fruits, grains, can be protected when freshly harvested or after being processed by (pre)-drying, wetting, crushing, grinding, pressing, or baking. Stored goods also include wood, including unprocessed wood (such as construction wood, utility poles, and fences) or wood in finished form (such as furniture). Stored goods of animal origin are, for example, hides, leather, furs, and hairs. The compounds and compositions of the present invention can prevent adverse effects, such as rot, decay, discoloration, fading, or the formation of mold.

[0611] Microorganisms capable of degrading or modifying industrial materials include, for example, bacteria, fungi, yeasts, algae, and slime organisms. The compounds and compositions of the present invention preferably resist fungi, in particular molds, fungi that discolor wood, and fungi that damage wood (Ascomycetes, Basidiomycetes, Deuteromycetes, and Zygomycetes), and resist slime organisms and algae.Examples include microorganisms of the following genera: Alternaria, such as Alternaria tenuis; Aspergillus, such as Aspergillus niger; Chaetomium, such as Chaetomium globosum; Coniophora, such as Coniophora puteana; Lentinus, such as Lentinus tigrinus; Penicillium, such as Penicillium glaucum; Polyporus, such as Polyporus versicolor; Aureobasidium, such as Aureobasidium pullulans; Sclerophoma, such as Sclerophoma pityophila; Trichoderma, such as Trichoderma viride; Ophiostoma spp., Ceratocystis spp., Humicola spp., Petriella spp., Trichurus spp., Coriolus spp., Gloeophyllum spp., Pleurotus spp., Poria spp., Serpula spp. and Tyromyces spp., Cladosporium spp., Paecilomyces spp., Mucor spp., Escherichia, such as Escherichia coli; Pseudomonas, such as Pseudomonas aeruginosa; Staphylococcus, such as Staphylococcus aureus; Candida spp. and Saccharomyces spp., such as Saccharomyces cerevisae.

[0612] Aspects of the teachings of the present invention can be further understood based on the following examples, which should not be construed as limiting the scope of the teachings of the present invention in any way.

[0613] Examples

[0614] Synthesis of the compound of formula (I)

[0615] Preparation Example (I)-1: Preparation of Ethyl N-[(4-bromo-5-cyano-3-methyl-2-thienyl)carbonyl]glycinate (Compound I.0024)

[0616] Step 1: Preparation of 4-Bromo-5-cyano-3-methylthiophene-2-carboxylic acid

[0617] To a 3.9 mL solution of 150 mg (0.86 mmol) of methyl 4-bromo-5-cyano-3-methylthiophene-2-carboxylate in tetrahydrofuran was added dropwise 0.7 mL of a 1.1 M aqueous lithium hydroxide solution (0.7 mmol). The reaction mixture was stirred at room temperature for 1 hour. The resulting reaction mixture was carefully acidified with 1.0 M aqueous hydrochloric acid at 0 °C and extracted with ethyl acetate. The combined organic layers were dried over anhydrous magnesium sulfate, filtered and concentrated under reduced pressure to give 142 mg (97% purity, 97% yield) of the title compound as a white solid. LogP = 2.05. (M+H) = 246.

[0618] Step 2: Preparation of Ethyl N-[(4-bromo-5-cyano-3-methyl-2-thienyl)carbonyl]glycinate (Compound I.0024)

[0619] In a 50 mL round-bottom flask under an inert atmosphere, a solution of 402 mg (2.37 mmol) of 2-chloro-1,3-dimethylimidazolium chloride in 5 mL of dichloromethane was added to a solution of 450 mg (1.82 mmol) of 4-bromo-5-cyano-3-methylthiophene-2-carboxylic acid and 1.37 mL (7.86 mmol) of N,N-diisopropylethylamine in 7 mL of dichloromethane. After stirring for 5 minutes, 333 mg (2.37 mmol) of glycine ethyl ester hydrochloride (1:1) was added, and the reaction mixture was stirred at room temperature for 1 hour. The resulting reaction mixture was concentrated under reduced pressure. The residue was purified by silica gel column chromatography (gradient of n-heptane / ethyl acetate) to give 516 mg (100% purity, 86% yield) of the title compound as a yellow solid. LogP = 2.40. (M+H) = 331.

[0620] Preparation Example (I)-2: Preparation of N-[(4,5-Dibromo-3-fluoro-2-thienyl)carbonyl]glycine (Compound I.0227)

[0621] In a first round-bottom flask, at room temperature, 95 μL (1.08 mmol) of oxalyl chloride and a drop of N,N-dimethylformamide were added to a solution of 300 mg (0.98 mmol) of 4,5-dibromo-3-fluorothiophene-2-carboxylic acid in 6.5 mL of anhydrous dichloromethane. After stirring at room temperature for 1 hour, the reaction mixture was concentrated under reduced pressure and dissolved in 2.3 mL of anhydrous 1,4-dioxane to obtain an acyl chloride solution. In a second round-bottom flask, 0.6 mL of 0.5 M aqueous sodium hydroxide solution (0.3 mmol) was added to a 1.5 mL aqueous solution of 220 mg (0.97 mmol) of glycine hydrochloride (1:1). The reaction mixture was stirred at room temperature for 3 hours and then slowly added to the previously prepared acyl chloride solution. The resulting reaction mixture was stirred at room temperature for 60 hours, diluted with water and carefully acidified with 37% (w / w) aqueous hydrochloric acid at 0 °C. The resulting precipitate was filtered off and the filtrate was concentrated under reduced pressure. The solid and the filtrate were collected and purified by preparative high performance liquid chromatography (gradient acetonitrile / aqueous formic acid (1%)), to give 100 mg (96% purity, 27% yield) of the title compound as a yellow solid. LogP = 1.97. (M+H) = 360.

[0622] Preparation Example (I)-3: Preparation of ethyl 1-{[(4,5-dibromo-3-iodo-2-thienyl)carbonyl]amino}cyclopropanecarbothioate (Compound I.0139)

[0623] Under an inert atmosphere, at room temperature, 106 μL (0.60 mmol) of N,N-diisopropylethylamine was added to a solution of 100 mg (2.20 mmol) of 1-{[(4,5-dibromo-3-iodo-2-thienyl)carbonyl]amino}cyclopropanecarboxylic acid in 2 mL of anhydrous dichloromethane, followed by 115 mg (0.30 mmol) of 1-[bis(dimethylamino)methylene]-1H-1,2,3-triazolo[4,5-b]pyridinium 3-oxide hexafluorophosphate. After stirring at room temperature for 15 minutes, 19 mg (0.30 mmol) of ethanethiol was added and the reaction mixture was stirred at room temperature for 18 hours. Saturated aqueous sodium bicarbonate solution was added and the resulting reaction mixture was extracted twice with dichloromethane. The combined organic layers were filtered through a silica gel column and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (gradient n-heptane / ethyl acetate) to give 53 mg (100% purity, 49% yield) of the title compound as a white solid. LogP = 3.96. (M+H) = 538.

[0624] Preparation Example (I)-4: Preparation of 1-{[(4,5-dibromo-3-fluoro-2-thienyl)carbonyl]amino}cyclobutanecarboxylic acid (Compound I.0172)

[0625] To a solution of 203 mg (0.47 mmol) of ethyl 1-{[(4,5-dibromo-3-fluoro-2-thienyl)carbonyl]amino}cyclobutanecarboxylate in 5 mL of tetrahydrofuran was added dropwise 1.04 mL of 1 M aqueous potassium hydroxide solution (1.04 mmol). The reaction mixture was stirred at room temperature for 76 hours. Then, the resulting reaction mixture was carefully acidified to pH 1 with 1.0 M aqueous hydrochloric acid at 0 °C and extracted three times with ethyl acetate. The combined organic layers were filtered through a Chem Elut TM column and concentrated under reduced pressure. The residue was purified by preparative high performance liquid chromatography (gradient acetonitrile / aqueous formic acid (1%)) to give 115 mg (98% purity, 59% yield) of the title compound as a yellow solid. LogP = 2.57. (M+H) = 400.

[0626] Preparation Example (I)-5: Preparation of methyl 1-{[(4,5-dibromo-3-fluoro-2-thienyl)thiocarbonyl]amino}cyclopropanecarboxylate (Compound I.0328)

[0627] Step 1: Preparation of methyl 1-{[(4,5-dibromo-3-fluoro-2-thienyl)carbonyl]amino}cyclopropanecarboxylate

[0628] In a 100 mL round-bottom flask under an inert atmosphere, a solution of 733 mg (4.33 mmol) of 2-chloro-1,3-dimethylimidazolinium chloride in 4.3 mL of dichloromethane was added to a solution of 1.0 g (3.33 mmol) of 4,5-dibromo-3-fluorothiophene-2-carboxylic acid and 2.50 mL (14.3 mmol) of N,N-diisopropylethylamine in 35 mL of dichloromethane. After stirring for 15 minutes, 1.0 g (6.66 mmol) of methyl 1-aminocyclopropanecarboxylate hydrochloride (1:1) was added and the reaction mixture was stirred at room temperature for 72 hours. Water was added and the resulting reaction mixture was extracted twice with dichloromethane. The combined organic layers were filtered through a Chem Elut TM column and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (gradient dichloromethane / ethyl acetate) to give 1.24 g (100% purity, 93% yield) of the title compound as a white solid. LogP = 2.77. (M+H) = 400.

[0629] Step 2: Preparation of methyl 1-{[(4,5-dibromo-3-fluoro-2-thienyl)thiocarbonyl]amino}cyclopropanecarboxylate (Compound I.0328)

[0630] To a solution of 265 mg (0.65 mmol) of methyl 1-{[(4,5-dibromo-3-fluoro-2-thienyl)carbonyl]amino}cyclopropanecarboxylate in 5 mL of 1,2-dimethoxyethane was added 267 mg (0.66 mmol) of Lawesson's reagent. The reaction mixture was stirred at 50 °C for 42 h. The resulting reaction mixture was diluted with dichloromethane and filtered through a basic

[0631] alumina column and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (gradient of n-heptane / ethyl acetate) to afford 158 mg (100% purity, 57% yield) of the title compound as a yellow solid. LogP = 3.91. (M+H) = 416.

[0632] Preparation Example (I)-6: Preparation of 1-{[(4,5-dibromo-3-fluoro-2-thienyl)thiocarbonyl]amino}cyclopropanecarboxylic acid (Compound I.0329)

[0633] To a solution of 271 mg (0.47 mmol) of methyl 1-{[(4,5-dibromo-3-fluoro-2-thienyl)thiocarbonyl]amino}cyclopropanecarboxylate in 7 mL of 1,2-dichloroethane was added 203 mg (0.47 mmol) of trimethyltin hydroxide. The reaction mixture was stirred at 60 °C for 18 h. The resulting reaction mixture was concentrated under reduced pressure, dissolved in ethyl acetoacetate, and washed 3 times with 1.0 M aqueous hydrochloric acid. The combined organic layers were filtered through a Chem Elut TM column and concentrated under reduced pressure. The residue was purified by preparative high performance liquid chromatography (gradient of acetonitrile / aqueous formic acid (1%)) to afford 135 mg (100% purity, 54% yield) of the title compound as a yellow solid. LogP = 2.95. (M+H) = 402.

[0634] Preparation Example (I)-7: Preparation of ethyl N-[(4,5-dichloro-3-cyano-2-thienyl)carbonyl]leucinate (Compound I.0279)

[0635] Step 1: Preparation of ethyl N-[(4,5-dichloro-3-iodo-2-thienyl)carbonyl]leucinate

[0636] In a 5 mL microwave reaction flask under an inert atmosphere, 102 mg (0.60 mmol) of 2-chloro-1,3-dimethylimidazolinium chloride dissolved in 1 mL of dichloromethane was added to a solution of 150 mg (0.46 mmol) of 4,5-dichloro-3-iodothiophene-2-carboxylic acid and 0.35 mL (2.00 mmol) of N,N-diisopropylethylamine in 2 mL of dichloromethane. After stirring for 5 minutes, 118 mg (0.60 mmol) of DL-leucine ethyl ester hydrochloride (1:1) was added, and the reaction mixture was stirred at room temperature for 2 hours. The resulting reaction mixture was concentrated under reduced pressure. The residue was purified by silica gel column chromatography (gradient of n-heptane / ethyl acetate) to give 183 mg (100% purity, 85% yield) of the title compound as a white solid. LogP = 5.04. (M+H) = 464.

[0637] Step 2: Preparation of N-[(4,5-dichloro-3-cyano-2-thienyl)carbonyl]leucine ethyl ester (Compound I.0279)

[0638] In a 5 mL microwave reaction flask under an inert atmosphere, 183 mg (0.39 mmol) of N-[(4,5-dichloro-3-iodo-2-thienyl)carbonyl]leucine ethyl ester and 42 mg (0.47 mmol) of copper(I) cyanide were added in sequence, and then degassed N,N-dimethylformamide (1.3 mL) was added. The reaction flask was sealed and the reaction mixture was stirred at 110 °C for 5 hours. The resulting reaction mixture was quenched with saturated aqueous sodium bicarbonate and extracted with ethyl acetate. The combined organic layers were filtered through a Chem Elut TM column and concentrated under reduced pressure. The residue was dissolved in dichloromethane, filtered through a silica gel column and concentrated under reduced pressure to give 125 mg (98% purity, 85% yield) of the title compound as a colorless oil. LogP = 4.05. (M+H) = 363.

[0639] Preparation Example (I)-8: Preparation of N-[(4,5-dibromo-3-fluoro-2-thienyl)carbonyl]glycine ethyl ester (Compound I.0449)

[0640] To a solution of 226 mg (0.72 mmol) of N-[(4-bromo-3-fluoro-2-thienyl)carbonyl]glycine ethyl ester in 6 mL of acetic acid was added 0.23 mL (4.37 mmol) of bromine. The reaction mixture was stirred at 70 °C for 2.5 hours. The resulting reaction mixture was quenched with ice at 0 °C, then saturated aqueous sodium thiosulfate was added and the mixture was extracted twice with dichloromethane. The combined organic layers were filtered through a Chem Elut TMColumn filtration and concentration under reduced pressure. The residue was purified by silica gel column chromatography (gradient n-heptane / ethyl acetate) to give 102 mg (100% purity, 36% yield) of the title compound as a yellow solid. LogP = 2.97. (M+H) = 388.

[0641] Preparation Example (I)-9: Preparation of ethyl N-[(4-chloro-3-fluoro-5-methyl-2-thienyl)carbonyl]glycinate (Compound I.0793)

[0642] To a solution of 50 mg (0.14 mmol) of ethyl N-[(5-bromo-4-chloro-3-fluoro-2-thienyl)carbonyl]glycinate in 1.5 mL of degassed 1,4-dioxane was added 25 mg (0.41 mmol) of trimethylcyclotriboroxane, 71 mg (0.22 mmol) of cesium carbonate, and 5.9 mg (7.2 μmol) of the (1:1) complex of [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium(II) with dichloromethane. The reaction mixture was stirred at 100 °C for 5 hours. The reaction mixture was diluted with water and extracted with ethyl acetate. The combined organic layers were washed with brine, filtered through a Chem Elut TM column and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (gradient n-heptane / ethyl acetate) to give 40 mg (100% purity, 98% yield) of the title compound as a white solid. LogP = 2.54. (M+H) = 280.

[0643] Preparation Example (I)-10: Preparation of N-(2-amino-2-oxoethyl)-4,5-dibromo-3-fluorothiophene-2-carboxamide (Compound I.0894)

[0644] Under an inert atmosphere and at room temperature, to a solution of 600 mg (1.66 mmol) of N-[(4,5-dibromo-3-fluoro-2-thienyl)carbonyl]glycine in 30 mL of N,N-dimethylformamide were added 133 mg (2.49 mmol) of ammonium chloride, 478 mg (2.49 mmol) of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, 225 mg (1.66 mmol) of 1-hydroxybenzotriazole, and 406 mg (3.32 mmol) of 4-(dimethylamino)pyridine. The reaction mixture was stirred at room temperature for 2 hours. The resulting reaction mixture was extracted with ethyl acetate. The combined organic layers were washed with brine, dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure. The residue was purified by preparative high performance liquid chromatography (gradient acetonitrile / aqueous ammonium bicarbonate solution [10 mmol / L]) to give 260 mg (99% purity, 43% yield) of the title compound as a white solid. LogP = 1.69. (M+H) = 359.

[0645] Preparation Example (I)-11: N-(2-Amino-2-sulfanylethyl)-4,5-dibromo-3-fluorothiophene-2-carboxamide (Compound I.0896)

[0646] Under an inert atmosphere, 270 mg (0.67 mmol) of Lawesson's reagent was added to a solution of 200 mg (0.56 mmol) of N-(2-amino-2-oxoethyl)-4,5-dibromo-3-fluorothiophene-2-carboxamide in 10 mL of toluene. The reaction mixture was stirred at 60 °C for 5 hours. The resulting reaction mixture was concentrated under reduced pressure, diluted with water and extracted with ethyl acetate. The combined organic layers were washed with brine, dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure. The residue was purified by preparative high performance liquid chromatography (gradient acetonitrile / aqueous formic acid solution (0.1%)) to give 80 mg (99% purity, 38% yield) of the title compound as a white solid. LogP = 2.25. (M+H) = 375.

[0647] Preparation Example (I)-12: Ethyl N-[(3-bromo-4,5-dichloro-2-thienyl)carbonyl]-2-methylalaninate (Compound I.1062)

[0648] Step 1: Preparation of Ethyl N-[(3-amino-4,5-dichloro-2-thienyl)carbonyl]-2-methylalaninate

[0649] A solution of 160 mg (0.94 mmol) of 2-chloro-1,3-dimethylimidazolinium chloride in 2 mL of dichloromethane was added to a solution of 154 mg (0.72 mmol) of 3-amino-4,5-dichlorothiophene-2-carboxylic acid and 0.55 mL (3.13 mmol) of N,N-diisopropylethylamine in 5 mL of dichloromethane. After stirring for 5 minutes, 1.0 g (6.66 mmol) of ethyl 2-methylalaninate hydrochloride (1:1) was added and the reaction mixture was stirred at room temperature for 48 hours. Water was added and the resulting reaction mixture was extracted twice with dichloromethane. The combined organic layers were filtered through a Chem Elut TM column and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (gradient heptane / ethyl acetate) to give 205 mg (100% purity, 87% yield) of the title compound as a white solid. LogP = 3.09. (M+H) = 325.

[0650] Step 2: Preparation of Ethyl N-[(3-bromo-4,5-dichloro-2-thienyl)carbonyl]-2-methylalaninate (Compound I.1062)

[0651] At 0 °C, tert-butyl nitrite (105 μL, 0.79 mmol) was added dropwise to a solution of copper(I) bromide (114 mg, 0.79 mmol) in 7 mL of anhydrous acetonitrile. The mixture was warmed to room temperature and 173 mg (0.53 mmol) of ethyl N-[(3-amino-4,5-dichloro-2-thienyl)carbonyl]-2-methylalaninate was added in portions. The reaction mixture was stirred at room temperature for 3 h. The reaction mixture was diluted with dichloromethane and carefully acidified with 1 M aqueous hydrochloric acid. The aqueous layer was extracted twice with dichloromethane. The combined organic layers were dried over anhydrous magnesium sulfate, filtered and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (gradient of n-heptane / ethyl acetate) to give 63 mg (100% purity, 30% yield) of the title compound as a white solid. LogP = 4.24. (M+H) = 388.

[0652] Synthesis of the compound of formula (II)

[0653] Preparation Example (II)-1: Preparation of methyl 5-chloro-4-cyano-3-methylthiophene-2-carboxylate (Compound II.028)

[0654] At 0 °C, tert-butyl nitrite (2.27 mL, 19.1 mmol) was added dropwise to a solution of copper(I) chloride (1.89 g, 19.1 mmol) in 45 mL of anhydrous acetonitrile. After stirring at 0 °C for 5 min, 2.50 g (12.7 mmol) of methyl 5-amino-4-cyano-3-methylthiophene-2-carboxylate was added in portions. The reaction mixture was warmed to room temperature and stirred for 18 h. The reaction mixture was diluted with dichloromethane and carefully acidified with 1 M aqueous hydrochloric acid. The aqueous layer was extracted twice with dichloromethane. The combined organic layers were dried over anhydrous magnesium sulfate, filtered and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (gradient of n-heptane / ethyl acetate) to give 1.15 g (100% purity, 42% yield) of the title compound as a white solid. LogP = 3.01. (M+H) = 216.

[0655] Preparation Example (II)-2: Preparation of 4-bromo-5-cyano-3-methylthiophene-2-carboxylic acid (Compound II.042)

[0656] To a solution of 150 mg (0.86 mmol) of methyl 4-bromo-5-cyano-3-methylthiophene-2-carboxylate in 3.9 mL of tetrahydrofuran was added dropwise 0.7 mL of 1.1 M aqueous lithium hydroxide solution (0.7 mmol). The reaction mixture was stirred at room temperature for 1 hour. The resulting reaction mixture was carefully acidified with 1.0 M aqueous hydrochloric acid at 0 °C and extracted with ethyl acetate. The combined organic layers were dried over anhydrous magnesium sulfate, filtered and concentrated under reduced pressure to give 142 mg (97% purity, 97% yield) of the title compound as a white solid. LogP = 2.05. (M+H) = 246.

[0657] Production Example (II)-3: Preparation of methyl 4-chloro-5-cyanothiophene-2-carboxylate (Compound II.046)

[0658] In a microwave reaction flask, to a solution of 100 mg (0.53 mmol) of 4-chloro-5-cyanothiophene-2-carboxylic acid in 3 mL of anhydrous dichloromethane at room temperature was added 60 μL (0.69 mmol) of oxalyl chloride and a drop of N,N-dimethylformamide. After stirring for 2 hours, 0.86 mL (21.3 mmol) of methanol was added and the reaction mixture was stirred at room temperature for 16 hours. The resulting mixture was filtered through a silica gel column and concentrated under reduced pressure. The resulting reaction mixture was stirred at room temperature for 60 hours, diluted with water and carefully acidified with 37% (w / w) aqueous hydrochloric acid at 0 °C. The resulting precipitate was filtered off and the filtrate was concentrated under reduced pressure. The residue was purified by silica gel column chromatography (gradient of n-heptane / ethyl acetate) to give 86 mg (99% purity, 79% yield) of the title compound as a white solid. LogP = 2.52. (M) = 201.

[0659] Production Example (II)-4: Preparation of methyl 4,5-dibromo-3-(difluoromethyl)thiophene-2-carboxylate (Compound II.055)

[0660] At room temperature, 2.7 g (11 mmol) of benzoyl peroxide and 35.7 g (200 mmol) of N-bromosuccinimide were added portionwise to a 500 mL carbon tetrachloride solution of 57 g (182 mmol) of methyl 4,5-dibromo-3-methylthiophene-2-carboxylate. The reaction mixture was heated under reflux for 18 hours. The precipitate was filtered off. The organic layer was washed with warm water, saturated aqueous sodium bicarbonate and brine, dried over anhydrous sodium sulfate and filtered. The filtrate was concentrated under reduced pressure to give 71 g of the corresponding bromomethyl compound as a yellow solid. 63.4 g (540 mmol) of 4-methylmorpholine N-oxide monohydrate were added portionwise to a 500 mL anhydrous acetonitrile solution of the latter (71 g, 181 mmol) at 0 °C. After stirring at room temperature for 16 hours, the reaction mixture was added dropwise to 2 L of 2 N aqueous hydrochloric acid and extracted with EtOAc. The organic layer was washed with water, saturated aqueous sodium bicarbonate and brine, dried over anhydrous sodium sulfate and filtered. The filtrate was concentrated under reduced pressure to give 23 g of the corresponding aldehyde as a yellow solid. 12 mL (99 mmol) of morpholine trifluoride were added dropwise to a 500 mL dichloromethane solution of 23 g (70 mmol) of the latter at 0 °C. The reaction mixture was stirred at room temperature for 18 hours. Then the reaction mixture was carefully added to an ice:water mixture and extracted twice with dichloromethane. The organic layer was washed twice with water, twice with brine, dried over anhydrous magnesium sulfate, filtered and concentrated under reduced pressure to give 8.9 g (14% yield) of the title compound. LogP = 3.81. (M) = 348.

[0661] Preparation Example (II)-5: Preparation of methyl 4,5-dichloro-3-cyanothiophene-2-carboxylate (Compound II.085)

[0662] At room temperature, 11.2 mL (88 mmol) of boron trifluoride diethyl etherate was added to a solution of 10 g (44 mmol) of methyl 3-amino-4,5-dichlorothiophene-2-carboxylate in 250 mL of diethyl ether. 7.4 mL (55 mmol) of isoamyl nitrite was added to the stirred mixture, and a gray precipitate slowly formed. The precipitate was then filtered off and washed with diethyl ether. The resulting solid was added portionwise at 15 °C to a stirred solution of 27.4 g (42 mmol) of potassium cyanide and 8.3 g (93 mmol) of copper(I) cyanide in 300 mL of water. The reaction mixture was stirred at room temperature for 16 hours. Ethyl acetate was poured into the stirred reaction mixture and the organic layer was separated. The aqueous layer was extracted twice with ethyl acetate. The combined organic layers were washed with water, dried over anhydrous magnesium sulfate, filtered and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (gradient of n-heptane / ethyl acetate) to give 2.24 g (21% yield) of the title compound as a white solid. LogP = 2.98. (M) = 235.

[0663] Preparation Example (II)-6: Preparation of ethyl 4,5-dichloro-3-cyanothiophene-2-carboxylate (Compound II.053)

[0664] Step 1: Preparation of ethyl 4,5-dichloro-3-iodothiophene-2-carboxylate

[0665] Under argon, at 0 °C, 2.39 mL (1.3 mmol) of a solution of 2,2,6,6-tetramethylpiperidinylmagnesium chloride lithium chloride complex (17% in tetrahydrofuran) was added dropwise to a solution of 225 mg (1.0 mmol) of ethyl 4,5-dichlorothiophene-2-carboxylate in 10 mL of anhydrous tetrahydrofuran. The reaction mixture was stirred at room temperature for 20 minutes. A solution of 508 mg (2.0 mmol) of iodine in 5 mL of anhydrous solution was added dropwise to the stirred mixture. The reaction mixture was stirred at room temperature for 18 hours. The resulting reaction mixture was quenched with saturated aqueous sodium thiosulfate and extracted with ethyl acetate. The combined organic layers were washed with water, dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure to give 368 mg (95% purity, 99% yield) of the title compound as a solid. LogP = 4.75. (M) = 350.

[0666] Step 2: Preparation of ethyl 4,5-dichloro-3-cyanothiophene-2-carboxylate (Compound II.053)

[0667] Under an inert atmosphere, 200 mg (0.57 mmol) of ethyl 4,5-dichloro-3-iodothiophene-2-carboxylate and 61 mg (0.68 mmol) of copper(I) cyanide were successively added to a 5 mL microwave reaction flask, and then degassed N,N-dimethylformamide (1.5 mL) was added. The reaction flask was sealed and the reaction mixture was stirred at 110 °C for 5 hours. The resulting reaction mixture was quenched with saturated aqueous sodium bicarbonate and extracted with dichloromethane. The combined organic layers were washed with water, dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (gradient of n-heptane / ethyl acetate) and preparative high performance liquid chromatography (gradient of acetonitrile / aqueous formic acid solution (0.1%)) to give 60 mg (100% purity, 42% yield) of the title compound as a white solid. LogP = 3.54. (M+Na) = 272.

[0668] Preparation Example (II)-7: Preparation of ethyl 5-bromo-4-chloro-3-methylthiophene-2-carboxylate (Compound II.033)

[0669] Step 1: Preparation of ethyl 5-amino-4-chloro-3-methylthiophene-2-carboxylate

[0670] A solution of 500 mg (2.25 mmol) of ethyl 5-amino-3-methylthiophene-2-carboxylate hydrochloride (1:1) in aqueous sodium bicarbonate was extracted twice with dichloromethane. The combined organic layers were washed with saturated aqueous sodium bicarbonate, filtered through a Chem Elut TM column and concentrated under reduced pressure. To a 4 mL solution of the residue in tetrahydrofuran at room temperature was added 331 mg (2.48 mmol) of N-chlorosuccinimide. The reaction mixture was stirred at room temperature for 18 hours. The resulting reaction mixture was quenched with saturated aqueous sodium bicarbonate and extracted with dichloromethane. The combined organic layers were filtered through a Chem Elut TM column and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (gradient of n-heptane / ethyl acetate) to give 260 mg (99% purity, 52% yield) of the title compound as a brown solid. LogP = 2.67. (M+H) = 220.

[0671] Step 2: Preparation of ethyl 5-bromo-4-chloro-3-methylthiophene-2-carboxylate (Compound II.033)

[0672] At 0 °C, tert-butyl nitrite (2.27 mL, 19.1 mmol) was added dropwise to a solution of copper(I) chloride (1.89 g, 19.1 mmol) in 45 mL of anhydrous acetonitrile. After stirring at 0 °C for 5 minutes, 2.50 g (12.7 mmol) of ethyl 5-amino-4-chloro-3-methylthiophene-2-carboxylate was added in portions. The reaction mixture was warmed to room temperature and stirred for 18 hours. The reaction mixture was diluted with dichloromethane and carefully acidified with 1 M aqueous hydrochloric acid. The aqueous layer was extracted twice with dichloromethane. The combined organic layers were dried over anhydrous magnesium sulfate, filtered and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (gradient of n-heptane / ethyl acetate) to give 1.15 g (100% purity, 42% yield) of the title compound as a white solid. LogP = 3.01. (M+H) = 216.

[0673] Preparation Example (II)-8: Preparation of 4,5-dichloro-3-cyanothiophene-2-carboxylic acid (Compound II.103)

[0674] At -78 °C, 1.40 mL (2.80 mmol) of a solution of lithium diisopropylamide (2.0 M in tetrahydrofuran) was added dropwise to a solution of 500 mg (2.80 mmol) of 4,5-dichlorothiophene-3-carbonitrile in 10 mL of anhydrous tetrahydrofuran. The reaction mixture was poured into a solution of dry ice in anhydrous tetrahydrofuran. The reaction mixture was concentrated under reduced pressure. The residue was carefully acidified to pH 1 with 1.0 M aqueous hydrochloric acid at 0 °C and extracted 3 times with ethyl acetate. The combined organic layers were dried and concentrated under reduced pressure. The residue was purified by preparative high performance liquid chromatography (gradient of acetonitrile / water) to give 327 mg (95% purity, 50% yield) of the title compound as a white solid. LogP = 1.61.

[0675]

[0676]

[0677]

[0678]

[0679]

[0680]

[0681]

[0682]

[0683]

[0684]

[0685]

[0686]

[0687]

[0688]

[0689]

[0690]

[0691]

[0692]

[0693]

[0694]

[0695]

[0696]

[0697]

[0698]

[0699]

[0700]

[0701]

[0702]

[0703]

[0704]

[0705]

[0706]

[0707]

[0708]

[0709]

[0710]

[0711]

[0712]

[0713]

[0714]

[0715]

[0716]

[0717]

[0718]

[0719]

[0720]

[0721]

[0722]

[0723]

[0724]

[0725]

[0726] Table II.1 shows, in a non-limiting manner, examples of compounds according to formula (II).

[0727]

[0728] Table II.1:

[0729]

[0730]

[0731]

[0732] In the above table, according to EEC directive 79 / 831 Annex V.A8, the measurement of the LogP value was carried out by HPLC (high performance liquid chromatography) on a reversed-phase column using the following method:

[0733] [a] The LogP value was determined by LC-UV measurement using an aqueous solution of 0.1% formic acid and acetonitrile as eluents (linear gradient from 10% acetonitrile to 95% acetonitrile) in the acidic range.

[0734] [b] The LogP value was determined by LC-UV measurement using an aqueous solution of 0.001 mol ammonium acetate and acetonitrile as eluents (linear gradient from 10% acetonitrile to 95% acetonitrile) in the neutral range.

[0735] [c] The LogP value was determined by LC-UV measurement using 0.1% phosphoric acid and acetonitrile as eluents (linear gradient from 10% acetonitrile to 95% acetonitrile) in the acidic range.

[0736] If more than one LogP value is obtained within the same method, all values are shown and separated by "+".

[0737] Calibration was carried out using straight-chain alkan-2-ones with known LogP values (having 3 to 16 carbon atoms) (measurement of the LogP value was carried out using retention time by linear interpolation between consecutive alkanones). The λ value was determined using the UV spectrum from 200 nm to 400 nm and the peak of the chromatographic signal. max value.

[0738] NMR-peak list

[0739] Table A-(I) provides the NMR data of formula (I) disclosed in the above table ( 1 H).

[0740] Table A-(II) provides the NMR data of formula (II) disclosed in the above table ( 1 H and 13 C).

[0741] For the selected examples 1 the 1 H-NMR data are shown in the form of a 1 1 H-NMR-peak list. For each signal peak, the δ value in ppm is listed, and the signal intensity is listed in parentheses. The δ value - signal intensity pairs are listed separated by semicolons.

[0742]

[0743] δ1(intensity 1); δ2(intensity 2);........; δ i (intensity i );........;δ n (intensity n

[0744] The intensity of the sharp signal is correlated with the height of the signal in the printed example of the NMR spectrum in centimeters and shows the true relationship of the signal intensity. Multiple peaks or the signal midpoint and their relative intensity compared to the strongest signal in the spectrum can be shown by the broad signal.

[0745] For calibration 1 of the chemical shift of the H spectrum, the chemical shift of tetramethylsilane and / or the solvent used is utilized, especially in the case of spectra measured in DMSO. Thus, in the NMR peak list, the tetramethylsilane peak can but does not have to appear.

[0746] 1 The list of H-NMR peaks is similar to a conventional 1 H-NMR printout and thus usually contains all the peaks listed in a conventional NMR description.

[0747] In addition, like a conventional 1 H-NMR printout, it can show the signals of the solvent, the signals of the stereoisomers of the target compound (which are also the subject of the present invention), and / or the signals of impurity peaks.

[0748] To show the compound signals in the δ range of the solvent and / or water, the conventional peaks of the solvent, such as the peak of DMSO in DMSO-D6 and the peak of water, are shown in 1 the H-NMR peak list and usually have an average high intensity.

[0749] The peaks of the stereoisomers of the target compound and / or the peaks of impurities usually have an average lower intensity than the peaks of the target compound (e.g., having a purity of >90%).

[0750] These stereoisomers and / or impurities can be typical for a specific preparation method. Thus, their peaks can help identify the reproducibility of the preparation method by means of a "by-product fingerprint".

[0751] When calculating the peaks of the target compound using known methods (MestreC, ACD simulation, and using expected values evaluated empirically), the person skilled in the art can optionally use an additional intensity filter to isolate the peaks of the target compound as needed. This separation is similar to the 1 pickup of relevant peaks in a conventional

[0752] H-NMR description. Other details of the NMR data description with a peak list can be found in the publication "Citation of NMR Peaklist Data within Patent Applications" of Research Disclosure Database Number 564025.

[0753] Table A-(I): NMR peak list of the compound of formula (I)

[0754]

[0755]

[0756]

[0757]

[0758]

[0759]

[0760]

[0761]

[0762]

[0763]

[0764]

[0765]

[0766]

[0767]

[0768]

[0769]

[0770]

[0771]

[0772]

[0773]

[0774]

[0775]

[0776]

[0777]

[0778]

[0779]

[0780]

[0781]

[0782]

[0783]

[0784]

[0785]

[0786]

[0787]

[0788]

[0789]

[0790]

[0791]

[0792]

[0793]

[0794]

[0795]

[0796]

[0797]

[0798]

[0799]

[0800]

[0801]

[0802]

[0803]

[0804]

[0805]

[0806]

[0807]

[0808]

[0809]

[0810]

[0811]

[0812]

[0813]

[0814]

[0815]

[0816]

[0817]

[0818]

[0819]

[0820]

[0821]

[0822]

[0823]

[0824]

[0825]

[0826]

[0827]

[0828]

[0829]

[0830]

[0831]

[0832]

[0833]

[0834]

[0835]

[0836]

[0837]

[0838]

[0839] Table A-(II): NMR peak list of the compound of formula (II)

[0840]

[0841]

[0842]

[0843]

[0844]

[0845]

[0846]

[0847]

[0848]

[0849]

[0850]

[0851]

[0852]

[0853] Biological data - compound of formula (I)

[0854] Example A described below shows that the compounds of formula (I) induce the expression of defense genes in Arabidopsis thaliana, and in particular stimulate the salicylic acid pathway. Thus, these compounds can induce host defense and thereby protect plants against a wide range of pathogens, including bacteria and fungi.

[0855] Examples B, C, D, E and F described below show the in vivo activity in plants of the compounds of formula (I) by stimulating plant defense against various pathogens infecting plants, including bacteria and fungi.

[0856] Examples G, H, I and J described below show in vitro cell tests in which the compounds of formula (I) are directly inactive against various pathogens, including bacteria and fungi, thus illustrating the mode of action of the compounds of formula (I) as plant host defense inducers.

[0857] Example A: Inducing the expression of defense genes in Arabidopsis thaliana

[0858] An Arabidopsis reporter plant containing the coding sequence of green fluorescent protein (GFP) linked to the salicylate-responsive promoter sequence of the PR1 (pathogenesis-related protein I) gene (AT2G14610) was grown for five days and then sprayed with the compound. At 3 days after spraying, plant fluorescence was measured using a MacroFluo instrument purchased from Leica Microsystems (Wetzlar, Germany). Fluorescence was quantified using Meta-Morph Microscopy Automation & Image Analysis software (Molecular Devices, Sunnyvale, Calif., United States).

[0859] The background fluorescence of mock-treated leaves was set to 1.00. Salicylic acid treatment (300 ppm) produced a relative fluorescence value of 2.70, thus demonstrating the effectiveness of the test system.

[0860] In this test, the following compounds of the present invention showed relative fluorescence values of at least greater than 2 at a compound concentration of 300 ppm: I.0003, I.0004, I.0005, I.0006, I.0012, I.0014, I.0016, I.0017, I.0018, I.0019, I.0021, I.0022, I.0023, I.0024, I.0026; I.0027, I.0029, I.0034, I.0035, I.0036, I.0038, I.0039, I.0041, I.0042, I.0043, I.0045, I.0046, I.0047, I.0048, I.0050, I.0052, I.0053, I.0054, I.0055, I.0059, I.0060, I.0062, I.0063, I.0064, I.0065, I.0066, I.0067, I.0068, I.0069, I.0070, I.0072, I.0073, I.0074, I.0075, I.0076, I.0077, I.0078, I.0079, I.0081, I.0083, I.0084, I.0085, I.0086; I.0087, I.0088, I.0089, I.0090, I.0091, I.0092, I.0093, I.0094, I.0096, I.0097, I.0098, I.0099, I.0100, I.0101, I.0102, I.0103, I.0105, I.0109; I.0113, I.0119, I.0120, I.0121; I.0122, I.0123, I.0124; I.0125, I.0126, I.0127, I.0128, I.0130, I.0131, I.0132, I.0133, I.0134, I.0135, I.0136, I.0137, I.0138, I.0140, I.0141, I.0142, I.0143, I.0144, I.0145, I.0146, I.0147, I.0148, I.0149, I.0150, I.0151, I.0152, I.0154, I.0155, I.0157, I.0159, I...

Claims

1. A compound of formula (I): wherein R 1 and R 2 are each independently selected from halogen, cyano, C1-C6-alkyl or C1-C6-haloalkyl, where R 1 or R 2 at least one of which is halogen; R 3 selected from hydrogen, halogen, cyano, C1-C6-alkyl or C1-C6-haloalkyl; Among them, R 1 、R 2 and R 3 and at least one of them is a cyano group; R 4 and R 5 are each independently selected from hydrogen; halogen; cyano; C1-C6-alkyl; C1-C6-hydroxyalkyl; C1-C6-haloalkyl; C3-C6-carbocycle; a 4-, 5- or 6-membered non-aromatic heterocyclic group containing 1 to 4 heteroatoms independently selected from oxygen, nitrogen and sulfur; -C(=O)-OH; -C(=O)-O-C1-C6-alkyl; -C1-C6-alkyl-C1-C6-alkoxy; -C1-C6-alkyl-C1-C6-haloalkyl; -C1-C6-alkyl-C3-C6-carbocycle; -C1-C6-alkyl-C6-C 10 -aryl; -C1-C6-alkyl-S-C1-C6-alkyl; -C1-C6-alkyl-C(=O)-NH2; -C1-C6-alkyl-C(=O)-NH(C1-C6-alkyl); -C1-C6-alkyl-C(=O)-N(C1-C6-alkyl)2; -C1-C6-alkyl-C(=O)-OH or -C1-C6-alkyl-C(=O)-O-C1-C6-alkyl, where the acyclic R 4 、R 5 groups may be substituted by one or more R w substituents, where the cyclic R 4 、R 5 groups may be substituted by one or more R x substituents, where at least one of R 4 and R 5 is hydrogen, C1-C6-alkyl or C3-C6-carbocycle, or R 4 and R 5 together with the carbon atom to which they are attached form a C3-C6-carbocycle or a 3- to 6-membered heterocycle, where the C3-C6-carbocycle and the 3- to 6-membered heterocycle may be substituted by one or more R x substituents, where R w is independently selected from nitro, hydroxy, cyano, carboxy, amino, thioalkyl or sulfamoyl, where R x is independently selected from halogen, nitro, hydroxy, cyano, carbonyl, amino, thioalkyl or sulfamoyl; R 6 and R 7 are independently selected from hydrogen or R 6 and R 7 together with the carbon atom to which they are attached form a C3-carbon ring; n is 0 or 1; W is oxygen or sulfur; Y is NR 8 , wherein R 8 is selected from hydrogen, C1-C6-alkyl, C1-C6-haloalkyl or C1-C6-alkoxy; and Z is selected from a cyano group, -C(=O)-OR a 、-C(=O)-SR a 、-C(=O)-NR b R c or -C(=S)-NR b R c , wherein R a is selected from hydrogen; C1-C6-alkyl; C1-C6-haloalkyl; C1-C6-cyanoalkyl; C2-C6-alkenyl; C2-C6-alkynyl; C3-C8-cycloalkyl; -C6-C 10 -aryl; -C1-C6-alkyl-C6-C 10 -aryl; a 4-, 5- or 6-membered non-aromatic heterocyclic group containing 1 to 4 heteroatoms independently selected from oxygen, nitrogen and sulfur; or -C1-C6-alkyl-C3-C8-cycloalkyl; or R a may together with R 4 and the atoms to which they are attached form a 4- to 7-membered heterocycle, wherein R b and R c are independently selected from hydrogen or C1-C6-alkyl.

2. The compound according to claim 1, wherein R 1 and R 2 are each independently selected from F, Cl, Br, I, cyano or CH3.

3. The compound according to claim 1, wherein R 1 and R 2 are each independently selected from F, Cl, Br or cyano.

4. The compound according to claim 1, wherein R 3 is selected from hydrogen, F, Cl, Br, I, cyano, CH3, CHF2 or CF3.

5. The compound according to claim 1, wherein R 3 is selected from hydrogen, F, Cl, Br, I, cyano or CH3.

6. The compound according to claim 1, wherein R 3 is selected from hydrogen, F, Cl, Br, cyano or CH3.

7. The compound according to claim 1, wherein R 4 is selected from hydrogen, C1-C6-alkyl, C1-C6-hydroxyalkyl, C3-C6-carbocycle, C(=O)-OH, -C(=O)-O-C1-C6-alkyl, -C1-C6-alkyl-C1-C6-alkoxy, -C1-C6-alkyl-C1-C6-haloalkyl, -C1-C6-alkyl-C3-C6-carbocycle, -C1-C6-alkyl-C6-C 10 -aryl, -C1-C6-alkyl-S-C1-C6-alkyl-, -C1-C6-alkyl-C(=O)-NH2, -C1-C6-alkyl-C(=O)-OH or -C1-C6-alkyl-C(=O)-O-C1-C6-alkyl, R5 is selected from hydrogen, C1-C6-alkyl or C3-C6-carbocycle; or R 4 and R 5 together with the carbon atom to which they are attached form a C3-C6-carbocycle.

8. The compound according to claim 1, wherein R 4 is selected from hydrogen, halogen, C1-C6-alkyl; C1-C6-haloalkyl, C3-C6-carbocycle, -C1-C6-alkyl-C1-C6-alkoxy, -C1-C6-alkyl-C1-C6-haloalkyl, -C1-C6-alkyl-C3-C6-carbocycle, -C1-C6-alkyl-C6-C 10 -aryl, C1-C6-alkyl-S-C1-C6-alkyl, -C1-C6-alkyl-C(=O)-NH2, -C1-C6-alkyl-C(=O)-OH or -C1-C6-alkyl-C(=O)-O-C1-C6-alkyl, R5 is selected from hydrogen, -C1-C6-alkyl or C3-C6-carbocycle; or R 4 and R 5 together with the carbon atom to which they are attached form a C3-C6-carbocycle.

9. The compound according to claim 1, wherein R 4 is selected from hydrogen, halogen, C1-C6-alkyl, C1-C6-haloalkyl, C3-C6-carbocycle, -C1-C6-alkyl-C1-C6-alkoxy, -C1-C6-alkyl-C1-C6-haloalkyl, -C1-C6-alkyl-C6-C 10 -aryl or -C1-C6-alkyl-S-C1-C6-alkyl, R5 is selected from hydrogen, C1-C6-alkyl or C3-C6-ring; or R 4 and R 5 together with the carbon atom to which they are attached form a C3-C6-carbocycle.

10. The compound according to claim 1, wherein n is 0.

11. The compound according to claim 1, wherein W is oxygen.

12. The compound according to claim 1, wherein Y is selected from NH or N - OCH3.

13. The compound according to claim 1, wherein Y is NH.

14. The compound according to claim 1, wherein Z is selected from cyano, -C(=O)-SR a , -C(=O)-OR a or -C(=O)-NR b R c .

15. The compound according to claim 1, wherein Z is selected from -C(=O)-OR a or -C(=O)-SR a .

16. The compound according to claim 1, wherein Z is selected from -C(=O)-OR a or -C(=O)-SR a , wherein R a is selected from hydrogen, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-cyanoalkyl, -C6-C 10 -aryl, -C1-C6-alkyl-C6-C 10 -aryl, or R a may together with R 4 and the atoms to which they are attached form a 4- to 7-membered heterocycle.

17. The compound according to claim 1, wherein Z is -C(=O)-OR a .

18. The compound according to claim 1, wherein R 1 and R 2 are each independently selected from halogen, cyano, C1-C6-alkyl or C1-C6-haloalkyl, where R 1 or R 2 at least one of which is halogen; R 3 selected from hydrogen, halogen, cyano, C1-C6-alkyl or C1-C6-haloalkyl; Among them, R 1 、R 2 and R 3 and at least one of them is a cyano group; R 4 and R 5 are each independently selected from hydrogen, halogen, C1-C6-alkyl, C1-C6-haloalkyl, C3-C6-carbocycle, -C1-C6-alkyl-C1-C6-alkoxy, -C1-C6-alkyl-C1-C6-haloalkyl, -C1-C6-alkyl-C6-C 10 -aryl, -C1-C6-alkyl-S-C1-C6-alkyl, -C1-C6-alkyl-C(=O)-NH2, -C1-C6-alkyl-C(=O)-NH(C1-C6-alkyl), -C1-C6-alkyl-C(=O)-N(C1-C6-alkyl)2, -C1-C6-alkyl-C(=O)-OH or -C1-C6-alkyl-C(=O)-O-C1-C6-alkyl, wherein acyclic R 4 , R 5 groups may be substituted by one or more R w substituents, wherein cyclic R 4 , R 5 groups may be substituted by one or more R x substituents, wherein at least one of R 4 and R 5 is hydrogen, C1-C6-alkyl or C3-C6-carbocycle, or R 4 and R 5 together with the carbon atom to which they are attached form a C3-C6-carbocycle, wherein the C3-C6-carbocycle may be substituted by one or more R x substituents, wherein R w is independently selected from nitro, hydroxy, cyano, carboxy, amino, sulfanyl or sulfamoyl, wherein R x is independently selected from halogen, nitro, hydroxy, cyano, carbonyl, amino, sulfanyl or sulfamoyl; R 6 and R 7 are each independently selected from hydrogen; n is 0 or 1; W is oxygen or sulfur; Y is NR 8 , where R 8 is selected from hydrogen, C1-C6-alkyl or C1-C6-haloalkyl; and Z is selected from -C(=O)-OR a or -C(=O)-SR a , where R a is selected from hydrogen, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-cyanoalkyl, C2-C6-alkenyl, C2-C6-alkynyl, C3-C8-cycloalkyl, C6-C 10 -aryl, -C1-C6-alkyl-C6-C 10 -aryl, a 4-, 5- or 6-membered non-aromatic heterocyclic group containing 1 to 4 heteroatoms independently selected from oxygen, nitrogen and sulfur, or -C1-C6-alkyl-C3-C8-cycloalkyl, or R a may together with R 4 and the atoms to which they are attached form a 4- to 7-membered heterocycle.

19. The compound according to claim 1, wherein R 1 and R 2 are each independently selected from halogen, cyano, C1-C6-alkyl or C1-C6-haloalkyl, where R 1 or R 2 at least one of which is halogen; R 3 selected from hydrogen, halogen, cyano, C1-C6-alkyl or C1-C6-haloalkyl; Among them, R 1 、R 2 and R 3 at least one of which is a cyano group; R 4 and R 5 are each independently selected from hydrogen, halogen, C1-C6-alkyl, C1-C6-haloalkyl, C3-C6-carbocycle, -C1-C6-alkyl-C1-C6-alkoxy, C1-C6-alkyl-C1-C6-haloalkyl, -C1-C6-alkyl-C6-C 10 -aryl or -C1-C6-alkyl-S-C1-C6-alkyl, where acyclic R 4 , R 5 groups may be substituted by one or more R w substituents, where cyclic R 4 , R 5 groups may be substituted by one or more R x substituents, where R 4 and R 5 at least one of which is hydrogen, C1-C6-alkyl or C3-C6-carbocycle, or R 4 and R 5 together with the carbon atom to which they are attached form a C3-C6-carbocycle, where the C3-C6-carbocycle may be substituted by one or more R x substituents, where R w is independently selected from nitro, hydroxy, cyano, carboxy, amino, thioalkyl or sulfamoyl, where R x is independently selected from halogen, nitro, hydroxy, cyano, carbonyl, amino, thioalkyl or sulfamoyl; R 6 and R 7 are independently selected from hydrogen; n is 0 or 1; W is oxygen or sulfur; Y is NR 8 , where R 8 is selected from hydrogen, C1-C6-alkyl or C1-C6-haloalkyl; and Z is selected from -C(=O)-OR a or -C(=O)-SR a , where R a is selected from hydrogen, C1-C6-alkyl, C1-C6-haloalkyl, C1-C6-cyanoalkyl, or R a can together with R 4 and the atoms to which they are attached form a 4- to 7-membered heterocycle.

20. A compound of formula (I) and its salts, Among them, R 1 、R 2 、R 3 、W、Y、R 4 、R 5 、n、R 6 、R 7 and Z are each independently defined as follows: 。 21. A composition comprising at least one compound of formula (I) according to any one of claims 1 to 20 and at least one agriculturally suitable adjuvant.

22. A method for controlling bacterial and / or fungal diseases, comprising the step of applying at least one compound of formula (I) according to any one of claims 1 to 20 or the composition according to claim 21 to a plant or the soil in which the plant grows.

23. A method for controlling bacterial and / or fungal diseases, comprising the step of applying at least one compound of formula (I) according to any one of claims 1 to 20 or the composition according to claim 21 to a plant part.

24. Use of the compound according to any one of claims 1 to 20 or the composition according to claim 21 for controlling bacterial and / or fungal diseases of plants.

25. Use of the compound according to any one of claims 1 to 20 or the composition according to claim 21 for controlling bacterial and / or fungal diseases on plant parts.

Images