RU2799335C2 - Substituted thiophenecarboxamides and analogues as antibacterial agents - Google Patents

Abstract

FIELD: organic chemistry.

SUBSTANCE: invention relates to a substituted thiophenecarboxamide of formula (II), where R¹, R² and R³ represent a chlorine atom; R⁴ is selected from a group consisting of a hydrogen atom, 2-methylpropyl, 1-methylpropyl, cyclopropyl, cyclopropyl substituted with alkenyl with 2–6 carbon atoms, benzyl and benzyl substituted with hydroxyl, and R⁵ represents a hydrogen atom; or R⁴ and R⁵ together with the carbon atom to which they are attached form cyclopropyl; R⁶ is selected from a group consisting of a hydrogen atom, alkyl with 1–6 carbon atoms, haloalkyl with 1–6 carbon atoms, cyanoalkyl with 1–6 carbon atoms, alkenyl with 2–6 carbon atoms, alkynyl with 2–6 carbon atoms, cycloalkyl with 3–8 carbon atoms, phenyl, benzyl, -C₁-C₆-alkyl-Si(C₁-C₆-alkyl)₃ and -C₁-C₆-alkyl-C₃-C₈-cycloalkyl; R⁷ represents a hydrogen atom or alkyl with 1–6 carbon atoms.

EFFECT: protection of plants from bacterial diseases, in particular, those caused by bacteria belonging to Xanthomonas genus.

4 cl, 7 tbl, 3 ex

Description

FIELD OF THE INVENTION

The present invention relates to substituted thiophenecarboxamides and their analogues, which can be used to protect plants from bacterial diseases, in particular those caused by bacteria belonging to the genus Xanthomonas.

PRIOR ART

Plant pathogenic bacteria can cause serious, economically detrimental diseases around the world. Bacteria belonging to the genus Xanthomonas are among the plant pathogenic bacteria considered to be the most destructive. They are the causative agents of various diseases on different host crops of agricultural importance. Examples of such diseases include bacterial spot (caused by Xanthomonas campestris pv. vesicatoria) affecting peppers and tomatoes, cruciferous black rot (caused by Xanthomonas campestris pv. campestris) affecting all cultivated cabbages (e.g. Brussels sprouts, kale, cauliflower and broccoli), citrus canker (caused by Xanthomonas axonopodis pv. citri) affecting citrus varieties (lime, orange, grapefruit, pomelo), leaf blight (caused by Xanthomonas oryzae pv. oryzae), rice attacking, leaf spot (caused by Xanthomonas arboricola pv. pruni), Prunus spp. (e.g. apricot, plum, peach), common fire blight (caused by Xanthomonas phaseoli) affecting beans, cassava fire blight (caused by Xanthomonas axonopodis pv. manihotis) affecting cassava, and angular leaf spot/fire blight (caused by Xanthomonas campestris pv. malvacearum), affecting cotton.

Bacterial plant diseases can be controlled in a variety of ways, including mainly the use of disease-resistant plant varieties and the use of bactericides (natural or synthetic). The crisis of antibiotic resistance in medicine and the emergence of some antibiotic resistant plant pathogens have spurred the development of alternatives to antibiotics to maintain their effectiveness and expand the range of disease control solutions. As a result, products have been developed that do not act directly on pathogenic bacteria, i.e. do not have a direct antibiotic effect, but that stimulate the plant's own defense system. These products are known as plant protection activators. Examples of plant protection activators include acibenzolar-S-methyl (sold as Bion® and Actigard®), 2,6-dichloroisonicotinic acid, β-aminobutyric acid, probenazole (Oryzemate®), salicylic acid, riboflavin, prohexadione-calcium, potassium phosphonate, harpin protein (Messenger®); and methyl jasmonate.

Although many different organic and inorganic compounds have been shown to activate induced resistance in plants, only a small number of products are currently commercially available.

Therefore, there remains a need to develop new chemicals and methods that can effectively combat bacterial diseases, in particular diseases caused by bacteria belonging to the genus Xanthomonas, at low dosages, while not interacting directly with these bacteria, so as to prevent the development resistance.

Because these chemicals do not interact directly with bacteria, they are unlikely to develop resistance to these chemicals.

The inventors have proven that new chemicals belonging to the class of substituted thiophenecarboxamide derivatives offer a solution to the above problem.

Certain substituted thiophenecarboxamide derivatives are known to be useful for controlling plant diseases. For example, US Pat. No. 5,534,541 discloses halothiophenecarboxylic acid derivatives that are useful in protecting plants from attack by plant damaging microorganisms such as fungi and bacteria, through direct action or systemic action. However, the authors of the present invention found that these compounds are ineffective against Xanthomonas campestris pv. campestris at low dosage.

Other examples of halothiophenecarboxylic acid derivatives are disclosed in WO2004/024692. These derivatives are considered effective in the fight against fungal diseases. They will exert their effect through direct action on undesirable micro-organisms, as well as through resistance-producing effects on plants. WO2004/024692 also suggests that these compounds might be useful in combating bacterial diseases, but provides no evidence for such activity.

BRIEF DESCRIPTION OF THE INVENTION

The present invention relates to the compounds of formula (II) disclosed in this document, as well as to methods and intermediates for their preparation.

The present invention also relates to a method for combating bacterial diseases disclosed in this document.

DEFINITIONS

The term "alkyl with 1-6 carbon atoms"("C ₁ -C ₆ -alkyl"), as used in this document, refers to a saturated, branched or straight hydrocarbon chain containing 1, 2, 3, 4, 5 or 6 atoms carbon. Examples of alkyl with 1-6 carbon atoms include, but are not limited to, methyl, ethyl, propyl (n-propyl), 1-methylethyl (isopropyl), butyl (n-butyl), 1-methylpropyl (sec-butyl), 2 -methylpropyl (isobutyl), 1,1-dimethylethyl (tert-butyl), pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, 1,1-dimethylpropyl, 1,2 -dimethylpropyl, hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl , 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl and 1-ethyl-2-methylpropyl. In particular, the specified hydrocarbon chain has 1, 2, 3 or 4 carbon atoms ("alkyl with 1-4 carbon atoms"("C ₁ -C ₄ -alkyl")), for example, methyl, ethyl, propyl, isopropyl, butyl , sec-butyl, isobutyl or tert-butyl.

The term "haloalkyl" as used herein is to be understood as preferably meaning branched and straight-chain alkyl as defined above, in which one or more hydrogen substituents are replaced by halogen in the same or different ways. Particularly preferably, said haloalkyl is, for example, chloromethyl, fluoropropyl, fluoromethyl, difluoromethyl, trichloromethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, bromobutyl, trifluoromethyl, iodoethyl and their isomers.

The term "cycloalkyl" as used herein refers to a non-aromatic monocyclic carbon-containing 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 groups.

The term "alkenyl" as used herein is to be understood as preferably meaning both branched and straight-chain alkenyl, e.g., vinyl, propen-1-yl, propen-2-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-methylprop-2-en-1-yl or 2- methylprop-1-en-1-yl group.

The term "alkynyl" as used herein is to be understood as preferably meaning branched and unbranched alkynyl, e.g., ethynyl, prop-1-yn-1-yl, but-1-yn-1-yl, but-2-yn- 1-yl or but-3-yn-1-yl group.

The term "aryl" as used herein 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. This ring system may be a monocyclic or fused polycyclic (eg, bicyclic or tricyclic) aromatic ring system. Examples of aryl include, but are not limited to, phenyl, azulenyl, naphthyl, and fluorenyl. In addition, it is understood that when said aryl group is substituted with one or more substituents, said substituent(s) may be located at any position on said aryl ring(s). In particular, when aryl is a phenyl group, said substituent(s) may occupy one or both of the ortho positions, one or both of the meta positions, or of the para position, or any combination of these positions. This definition also applies to aryl as part of a compound substituent (eg, aryloxy).

The term "arylalkyl" as used herein refers to alkyl with 1-6 carbon atoms substituted with aryl, as defined herein. An example of arylalkyl includes a benzyl group (-CH ₂ -C ₆ H ₅ ).

DETAILED DESCRIPTION OF THE INVENTION

Compounds of formula (II) as shown below have been found to be effective against diseases caused by bacteria of the genus Xanthomonas at low dosages (i.e., dosages as low as 31 ppm) without being directly bactericidal.

The present invention relates to compounds of formula (II):

wherein

R ¹ , R ² and R ³ represent a chlorine atom;

R ⁴ is selected from the group consisting of a hydrogen atom, 2-methylpropyl, 1-methylpropyl, cyclopropyl, cyclopropyl substituted with 2-6 carbon alkenyl, arylalkyl and hydroxyl-substituted arylalkyl, and R ⁵ represents a hydrogen atom; or

R ⁴ and R ⁵ together with the carbon atom to which they are attached form cyclopropyl;

R ⁶ is selected from the group consisting of hydrogen atom, C 1-6 alkyl, C 1-6 haloalkyl, C 1-6 cyanoalkyl, C 2-6 alkenyl, C 2-6 alkynyl , cycloalkyl with 3-8 carbon atoms, aryl, arylalkyl, -C ₁ -C ₆ -alkyl-Si (C ₁ -C ₆ -alkyl) ₃ and -C ₁ -C ₆ -alkyl-C ₃ -C ₈ -cycloalkyl ;

R ⁷ represents a hydrogen atom or alkyl with 1-6 carbon atoms.

Not covered herein are compounds resulting from combinations that are contrary to the laws of nature and which a person skilled in the art would therefore exclude on the basis of his/her expert knowledge. For example, cyclic structures containing three or more neighboring oxygen atoms are excluded.

Depending on the nature of the substituents, the compound of formula (II) may be present in the form of various stereoisomers. These stereoisomers are, for example, enantiomers, diastereomers, atropisomers or geometric isomers. Accordingly, the invention covers both pure stereoisomers and any mixture of these isomers. If a compound can be present in two or more tautomeric forms existing in equilibrium, then reference to the compound by a single tautomeric description should be considered to include all tautomeric forms.

Any of the compounds of the present invention may also exist in one or more geometric isomer forms, depending on the number of double bonds in the compound. Geometric isomers, according to the nature of the substituents on the double bond or ring, may be present in cis (= Z-) or trans (= E-) form. Thus, the invention applies equally to all geometric isomers and to all possible mixtures in all proportions.

The compound of formula (II) may suitably be in its free form, salt form, N-oxide form, or solvate (eg hydrate) form.

Depending on the nature of the substituents, the compound of formula (II) may be present in the form of a free compound and/or a salt thereof, such as an agrochemically active salt.

Agrochemically active salts include acid addition salts of inorganic and organic acids, as well as salts of conventional 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 bisulfate and potassium bisulfate. Suitable 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 containing from 6 to 20 carbon atoms, alkyl monoesters of sulfuric acid, alkyl sulfonic acids (sulfonic acids having linear or branched alkyl radicals containing from 1 to 20 carbon atoms) , arylsulfonic acids or aryldisulfonic acids (aromatic radicals such as phenyl and naphthyl which contain one or two sulfonic acid groups), alkylphosphonic acids (phosphonic acids having linear or branched alkyl radicals containing from 1 to 20 carbon atoms), arylphosphonic acids or aryl diphosphonic acids (aromatic radicals such as phenyl and naphthyl which contain one or two phosphonic acid radicals), where the alkyl and aryl radicals may contain other substituents, e.g. p-toluenesulfonic acid, salicylic acid, p-aminosalicylic acid, 2- phenoxybenzoic acid, 2-acetoxybenzoic acid and so on.

Solvates of compounds of formula (II) or their salts are stoichiometric compositions of compounds with solvents.

The compounds of formula (II) may exist in a variety of crystalline and/or amorphous forms. Crystalline forms include unsolvated crystalline forms, solvates and hydrates.

In some embodiments, in formula (I) above, R ⁴ is selected from the group consisting of hydrogen, 2-methylpropyl, 1-methylpropyl, cyclopropyl, cyclopropyl substituted with 2-6 carbon alkenyl, arylalkyl, and hydroxyl-substituted arylalkyl, and R ⁵ represents a hydrogen atom.

Non-limiting examples of suitable R ⁴ groups include any of the R ⁴ groups disclosed in the "R ⁴ " column of Table II.1.

In some embodiments, in formula (II) above, R ⁶ is selected from the group consisting of hydrogen, C 1-6 alkyl, C 1-6 haloalkyl, C 1-6 cyanoalkyl, 2- 6 carbon atoms, alkynyl with 2-6 carbon atoms, cyclopropyl, phenyl, benzyl, -C ₁ -C ₆ -alkyl-Si(C ₁ -C ₆ -alkyl) ₃ and -C ₁ -C ₆ -alkylcyclopropyl.

Non-limiting examples of suitable R ⁶ groups include any of the R ⁶ groups disclosed in the "R ⁶ " column of Table II.1.

In some embodiments, in formula (II) above, R ⁷ is hydrogen or methyl.

The above definitions of R ⁴ , R ⁶ and R ⁷ can be combined in various ways to obtain subclasses of compounds according to the invention.

Non-limiting examples of connection subclasses include the subclasses described herein below.

In some embodiments, the compounds of the present invention are compounds of formula (II):

wherein

R ¹ , R ² and R ³ represent a chlorine atom;

R ⁴ represents a hydrogen atom or isobutyl, and R ⁵ represents a hydrogen atom; or

R ⁴ and R ⁵ together with the carbon atom to which they are attached form cyclopropyl;

R ⁶ is hydrogen or C 1 -C 6 alkyl, preferably hydrogen or C 1 -C 4 alkyl, more preferably hydrogen, methyl or ethyl.

The compounds of formula (II) can be used to combat bacterial diseases, in particular to combat diseases caused by bacteria belonging to the genus Xanthomonas.

Methods for the preparation of compounds of Formula (II)

The present invention relates to processes for the preparation of compounds of formula (II). Compounds of formula (II) can be prepared in various ways in analogy to known methods (see references in this text) and using one or more of the following synthetic routes described below in this document and in the experimental part.

General routes for the synthesis of compounds of formula (II)

Unless otherwise indicated, hereinafter R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ have the same meaning as indicated above for the compounds of formula (II).

Method A2

Compounds of formula (II), as defined herein, can be prepared by method A2, which includes the step of reacting a compound of formula (XIV), or one of its salts, with a compound of formula (XV), or one of its salts, as illustrated by the following scheme reactions:

moreover, U ¹ represents a halogen atom, a hydroxy group or a C ₁ -C ₆ -alkoxy group.

If U ¹ represents a hydroxy group, then method A2 is advantageously carried out in the presence of a condensing agent. Suitable condensing agents may be selected from a non-limiting list consisting of an acid halide forming component such as phosgene, phosphorus tribromide, phosphorus trichloride, phosphorus pentachloride, phosphorus trichloride oxide, oxalyl chloride, or thionyl chloride; an anhydride forming component 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 conventional condensing agents such as phosphorus pentoxide, polyphosphoric acid, bis(2-oxo -3-oxazolidinyl)phosphinyl chloride, 1-[bis(dimethylamino)methylene]-1H-1,2,3-triazolo[4,5-b]pyridinium-3-oxide hexafluorophosphate (HATU), 2-(1H-benzotriazole- 1-yl)-1,1,3,3-tetramethylaminium tetrafluoroborate (TBTU), (1-cyano-2-ethoxy-2-oxoethylideneaminooxy)dimethylaminomorpholinocarbenium hexafluorophosphate, N,N'-carbonyldiimidazole, 2-ethoxy-N-ethoxycarbonyl- 1,2-dihydroquinoline (EEDQ), triphenylphosphine/tetrachloromethane, 4-(4,6-dimethoxy[1.3.5]triazin-2-yl)-4-methylmorpholinium chloride hydrate, bis(2-oxo-3-oxazolidinyl)phosphinyl chloride (BOP-Cl), bromotripyrrolidinophosphonium hexafluorophosphate (PyBroP), 2-chloro-1,3-dimethylimidazolinium chloride (DMC), or propanephosphonic anhydride (T3P).

If U ¹ represents a halogen atom, then method A2 is preferably carried out in the presence of an acid-binding agent. Suitable acid binding agents for the implementation of method A2 in each case are all inorganic and organic bases which are customary for such reactions. Preference is given to alkali metal carbonates such as cesium carbonate, sodium carbonate, potassium carbonate, potassium bicarbonate, sodium bicarbonate, alkaline earth metal acetates such as sodium acetate, potassium acetate, calcium acetate, as well as tertiary amines such as trimethylamine, triethylamine, diisopropylethylamine , tributylamine, N,N-dimethylaniline, N-methylpiperidine, N,N-dimethylpyridine-4-amine, diazabicyclooctane (DABCO), diazabicyclononene (DBN) or diazabicycloundecene (DBU), or aromatic bases such as pyridine.

If U ¹ is a C ₁ -C ₆ alkoxy group, then Method A2 can be carried out with an excess of the amine component, optionally in the presence of a Lewis acid such as trimethylaluminum.

If necessary, method A2 can be carried out in the presence of a base and, if necessary, in the presence of a solvent, preferably under anhydrous conditions.

Suitable solvents for carrying out method A2 are not particularly limited. They may be conventional inert organic solvents, provided that they do not dissolve the compound so as to react with it or exhibit any particular interaction with it. Preference is given to using, if desired, halogenated, aliphatic, alicyclic or aromatic hydrocarbons such as petroleum ether, pentane, hexane, heptane, cyclohexane, methyl cyclohexane, benzene, toluene, xylene, decalin, ISOPAR™ E or ISOPAR™ 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- or isobutyronitrile or benzonitrile; amides such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric acid 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 their mixtures.

Method A2 can be carried out in an inert atmosphere such as an argon or nitrogen atmosphere. When carrying out method A2 per mol of the compound of formula (XIV), 1 mol or an excess of the compound of formula (XV) and from 1 to 5 mol of base can be used. It is also possible to use the reaction components in other ratios. Processing is carried out by known methods.

Compounds of formula (XV) are commercially available or can be prepared by well known methods.

Compounds of formula (XIV) in which U ¹ is hydroxy are commercially available and can be prepared from compounds of formula (XIV) in which U ¹ is C ₁ -C ₆ alkoxy by well-known methods such as basic hydrolysis, or can be obtained using known methods (Beilstein J. Org. Chem. 2007, 3, no. 23).

Compounds of formula (XIV) in which U ¹ is halogen are commercially available or can be prepared from compounds of formula (XIV) in which U ¹ is hydroxy by well-known methods.

Compounds of formula (XIV) in which U ¹ is C ₁ -C ₆ alkoxy can be prepared from compounds of formula (XIV) in which U ¹ is hydroxy by well-known methods.

Method B2

Compounds of formula (II) as defined herein can be prepared by Method B2 from a compound of formula (XVI) or one of its salts by carrying out a chlorination reaction as illustrated in the following reaction scheme:

moreover, U ¹⁰ , U ¹¹ and U ¹² independently of each other represent a hydrogen atom or a chlorine atom, provided that at least one of the U ¹⁰ , U ¹¹ or U ¹² represents a hydrogen atom.

Method B2 can be carried out according to known methods (WO2007098356).

Method B2 is carried out in the presence of a chlorinating agent and, if necessary, in the presence of a solvent.

Suitable chlorinating agents for carrying out method B2 are not particularly limited, provided that they are used for chlorination. Examples of chlorinating agents include N-chlorosuccinimide, sulfuryl chloride and 1,3-dichloro-5,5-dimethyl-2,4-imidazolidinedione.

Suitable solvents for carrying out method B2 are not particularly limited. They may be conventional inert organic solvents, provided that they do not dissolve the compound so as to react with it or exhibit any particular interaction with it. Suitable solvents may be, for example, those disclosed in connection with Method A2. It may also be advantageous to use an organic acid, such as acetic acid, as a solvent or co-solvent to carry out process B2.

Method C2

Compounds of formula (II) as defined herein can be prepared by Method C2, comprising the step of diazotizing a compound of formula (XVII) or one of its salts, followed by aromatic substitution to obtain a compound of formula (II), as illustrated in the following reaction scheme :

where U ¹³ , U ¹⁴ and U ¹⁵ independently of each other represent an amino group or a chlorine atom, provided that at least one of U ¹³ , U ¹⁴ or U ¹⁵ represents an amino group.

Method C2 can be carried out according to known methods (The Chemistry of diazonium and diazo groups; Saul Patai; Wiley-Interscience; 1978; 288-280 and 645-657; Account of Chemical Research (2018), 51, 496 and cited therein links).

Compounds of formula (XVII) or one of their salts as defined herein can be prepared by a process comprising the step of deprotecting a compound of formula (XVIII) or one of its salts as illustrated in the following reaction scheme:

Where

U ¹³ , U ¹⁴ and U ¹⁵ independently of each other represent an amino group or a chlorine atom, provided that only one of U ¹³ , U ¹⁴ or U ¹⁵ represents an amino group,

U ¹⁶ , U ¹⁷ and U ¹⁸ independently of each other represent a protected amino group or a chlorine atom, provided that at least one of U ¹⁶ , U ¹⁷ or U ¹⁸ represents a protected amino group.

Examples of amino protecting groups include benzyl group, 4-methoxybenzyl group, allyl group, unsubstituted or substituted C ₁ -C ₆ alkylsulfonyl, trifluoromethylsulfonyl, unsubstituted or substituted phenylsulfonyl, unsubstituted or substituted C ₁ -C ₆ alkoxycarbonyl, unsubstituted or substituted benzyloxycarbonyl , allyloxycarbonyl, an acetyl group, or a trifluoroacetyl group.

The deprotection process can be carried out according to known deprotection methods (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 environment (eg, with hydrochloric acid or trifluoroacetic acid). Benzyl protecting groups can be removed by hydrogenolysis with hydrogen in the presence of a catalyst (eg palladium on activated carbon). The trifluoroacetyl group can be removed in a basic medium (eg with potassium carbonate or lithium hydroxide).

Compounds of formula (XVII) can also be prepared from compounds of formula (XIX) and compounds of formula (XVIII) can be prepared from compounds of formula (XX) by reaction with a compound of formula (XV) under the conditions described in Method A2:

where U ¹³ , U ¹⁴ , U ¹⁵ , U ¹⁶ , U ¹⁷ and U ¹⁸ are as defined herein, and U ¹ represents a halogen atom, a hydroxy group or a C ₁ -C ₆ alkoxy group.

Compounds of formula (XIX) and compounds of formula (XX) are commercially available or can be prepared using well known methods with reaction conditions similar to those described for the preparation of compounds of formula (XIV).

Compounds of formula (II) or one of their salts, in which R ⁶ represents a hydrogen atom, can be obtained from compounds of formula (II), where R ⁶ represents alkyl with 1-6 carbon atoms, haloalkyl with 1-6 carbon atoms , cyanoalkyl with 1-6 carbon atoms, alkenyl with 2-6 carbon atoms, alkynyl with 2-6 carbon atoms, cycloalkyl with 3-8 carbon atoms, aryl, arylalkyl, -C ₁ -C ₆ -alkyl-Si (C ₁ -C ₆ -alkyl) ₃ and -C ₁ -C ₆ -alkylcyclopropyl, by well-known methods such as basic hydrolysis.

Compounds of formula (II) wherein R ⁶ is C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 cyanoalkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl , cycloalkyl with 3-8 carbon atoms, aryl, arylalkyl, -C ₁ -C ₆ -alkyl-Si(C ₁ -C ₆ -alkyl) ₃ and -C _{1 -C 6} -alkylcyclopropyl, can be obtained from compounds of formula ( II) or one of their salts, where R ⁶ represents a hydrogen atom, by well known methods.

Compounds of formula (II) or one of its salts in which R ⁷ is C 1 -C 6 alkyl can be prepared from compounds of formula (II) where R ⁷ is hydrogen by well-known methods such as alkylation using a base such as sodium hydride and a C ₁ -C ₆ alkyl halide.

The intermediates disclosed herein may be effective in controlling bacteria and/or fungi.

Intermediates for the preparation of compounds of formula (II)

The present invention relates to intermediates for the preparation of compounds of formula (II).

Unless otherwise indicated, hereinafter R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ have the same meaning as indicated above for the compounds of formula (II).

Compounds of formulas (XVIa) and (XVIb) are provided:

in which

R ¹ , R ² and R ³ represent a chlorine atom;

R ⁴ is selected from the group consisting of hydrogen, 2-methylpropyl, 1-methylpropyl, cyclopropyl, cyclopropyl substituted with 2-6 carbon alkenyl, arylalkyl and hydroxyl-substituted arylalkyl, and

R ⁵ represents a hydrogen atom; or

R ⁴ and R ⁵ together with the carbon atom to which they are attached form cyclopropyl;

R ⁶ is selected from the group consisting of hydrogen atom, C 1-6 alkyl, C 1-6 haloalkyl, C 1-6 cyanoalkyl, C 2-6 alkenyl, C 2-6 alkynyl , cycloalkyl with 3-8 carbon atoms, aryl, arylalkyl, -C ₁ -C ₆ -alkyl-Si (C ₁ -C ₆ -alkyl) ₃ and -C ₁ -C ₆ -alkyl-C ₃ -C ₈ -cycloalkyl .

Compounds of formula (XVIc):

R ¹ , R ² and R ³ represent a chlorine atom;

R ⁴ is selected from the group consisting of hydrogen, 2-methylpropyl, 1-methylpropyl, cyclopropyl, cyclopropyl substituted with 2-6 carbon alkenyl, arylalkyl and hydroxyl-substituted arylalkyl, and

R ⁵ represents a hydrogen atom; or

R ⁴ and R ⁵ together with the carbon atom to which they are attached form cyclopropyl;

R ⁶ is selected from the group consisting of hydrogen atom, C 1-6 alkyl, C 1-6 haloalkyl, C 1-6 cyanoalkyl, C 2-6 alkenyl, C 2-6 alkynyl , cycloalkyl with 3-8 carbon atoms, aryl, arylalkyl, -C ₁ -C ₆ -alkyl-Si (C ₁ -C ₆ -alkyl) ₃ and -C ₁ -C ₆ -alkyl-C ₃ -C ₈ -cycloalkyl ;

provided that the compound of formula (XVIc) is not:

N-[(4,5-dichloro-2-thienyl)carbonyl]glycine [138326-45-1],

N-[(4,5-dichloro-2-thienyl)carbonyl]isoleucine [138326-47-3],

N-[(4,5-dichloro-2-thienyl)carbonyl]leucine [138326-54-2],

methyl N-[(4,5-dichloro-2-thienyl)carbonyl]leucinate [138326-32-6],

methyl N-[(4,5-dichloro-2-thienyl)carbonyl]isoleucinate [138326-33-7],

2,2,2-trifluoroethyl-N-[(4,5-dichloro-2-thienyl)carbonyl]valinate [138326-35-9],

2,2,2-trifluoroethyl-N-[(4,5-dichloro-2-thienyl)carbonyl]leucinate [138326-36-0], and

2,2,2-trifluoroethyl-N-[(4,5-dichloro-2-thienyl)carbonyl]isoleucinate [138326-37-1].

Compounds of formulas (XVIIa), (XVIIb) and (XVIIc) are provided:

in which

R ¹ , R ² and R ³ represent a chlorine atom;

R ⁴ is selected from the group consisting of hydrogen, 2-methylpropyl, 1-methylpropyl, cyclopropyl, cyclopropyl substituted with 2-6 carbon alkenyl, arylalkyl and hydroxyl-substituted arylalkyl, and

R ⁵ represents a hydrogen atom; or

R ⁴ and R ⁵ together with the carbon atom to which they are attached form cyclopropyl;

R ⁶ is selected from the group consisting of hydrogen atom, C 1-6 alkyl, C 1-6 haloalkyl, C 1-6 cyanoalkyl, C 2-6 alkenyl, C 2-6 alkynyl , cycloalkyl with 3-8 carbon atoms, aryl, arylalkyl, -C ₁ -C ₆ -alkyl-Si (C ₁ -C ₆ -alkyl) ₃ and -C ₁ -C ₆ -alkyl-C ₃ -C ₈ -cycloalkyl ;

where R ⁴ is selected from the group consisting of a hydrogen atom, 2-methylpropyl, 1-methylpropyl, cyclopropyl, cyclopropyl substituted with alkenyl with 2-6 carbon atoms, arylalkyl and arylalkyl substituted with hydroxyl, and R ⁵ represents a hydrogen atom if R ⁶ represents a hydrogen atom or alkyl with 1-6 carbon atoms.

Compounds of formulas (XVIIIa), (XVIIIb) and (XVIIIc) are provided:

in which

R ¹ , R ² and R ³ represent a chlorine atom;

R ⁴ is selected from the group consisting of hydrogen, 2-methylpropyl, 1-methylpropyl, cyclopropyl, cyclopropyl substituted with 2-6 carbon alkenyl, arylalkyl and hydroxyl-substituted arylalkyl, and

R ⁵ represents a hydrogen atom; or

R ⁴ and R ⁵ together with the carbon atom to which they are attached form cyclopropyl;

R ⁶ is selected from the group consisting of hydrogen atom, C 1-6 alkyl, C 1-6 haloalkyl, C 1-6 cyanoalkyl, C 2-6 alkenyl, C 2-6 alkynyl , cycloalkyl with 3-8 carbon atoms, aryl, arylalkyl, -C ₁ -C ₆ -alkyl-Si (C ₁ -C ₆ -alkyl) ₃ and -C ₁ -C ₆ -alkyl-C ₃ -C ₈ -cycloalkyl ;

V represents a benzyl group, a 4-methoxybenzyl group, an allyl group, an unsubstituted or substituted C ₁ -C ₆ alkoxycarbonyl, an unsubstituted or substituted benzyloxycarbonyl, an allyloxycarbonyl, an acetyl group, or a trifluoroacetyl group;

where R ⁴ is selected from the group consisting of a hydrogen atom, 2-methylpropyl, 1-methylpropyl, cyclopropyl, cyclopropyl substituted with alkenyl with 2-6 carbon atoms, arylalkyl and arylalkyl substituted with hydroxyl, and R ⁵ represents a hydrogen atom if R ⁶ represents a hydrogen atom or alkyl with 1-6 carbon atoms.

Compounds of formulas (XIXa), (XIXb) and (XIXc) are provided:

in which

R ¹ , R ² and R ³ represent a chlorine atom;

U ^1a represents a hydroxy group or a C ₁ -C ₆ -alkoxy group, provided that the compound of formula (XIXc) does not represent:

methyl 3-amino-4,5-dichlorothiophene-2-carboxylate [1621488-35-4].

Compounds of formulas (XXa), (XXb) and (XXc) are provided:

in which

R ¹ , R ² and R ³ represent a chlorine atom;

V represents a benzyl group, a 4-methoxybenzyl group, an allyl group, an unsubstituted or substituted C ₁ -C ₆ alkoxycarbonyl, an unsubstituted or substituted benzyloxycarbonyl, an allyloxycarbonyl, an acetyl group, or a trifluoroacetyl group; And

U ^1a represents a hydroxy group or a C ₁ -C ₆ -alkoxy group, provided that the compound of formula (XXc) is not:

3-acetamido-4,5-dichlorothiophene-2-carboxylic acid [2090448-72-7],

methyl 3-acetamido-4,5-dichlorothiophene-2-carboxylate [632356-39-9], and

methyl 4,5-dichloro-3-[(methoxycarbonyl)amino]thiophene-2-carboxylate [35707-28-9].

The disclosed intermediates may be effective against bacteria and/or fungi.

Compositions and compositions

The present invention further relates to a composition, in particular a composition for combating plant diseases caused by bacteria of the genus Xanthomonas, comprising one or more of the compounds of formula (II) disclosed herein above, and any mixtures thereof.

The composition typically contains at least one compound of formula (II) and at least one agricultural adjuvant, eg carrier(s) and/or surfactant(s).

The carrier is a solid or liquid, natural or synthetic, organic or inorganic substance, which is usually inert. The carrier generally improves the application of the compounds to, for example, plants, plant parts or seeds. Examples of suitable solid carriers include, but are not limited to, ammonium salts, natural rock flours such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite and diatomaceous earth, and synthetic rock flours such as fumed silica. , aluminum oxide and silicates. Examples of commonly used solid carriers for the preparation of granules include, but are not limited to, ground and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, synthetic granules from inorganic and organic flours, and granules from organic material such as paper, sawdust, coconut shells, 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 aromatic and non-aromatic hydrocarbon classes (such as cyclohexane, paraffins, alkylbenzenes, xylene, toluene, alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes or methylene chloride) , alcohols and polyols (which, if desired, can also be substituted, etherized and/or esterified, such as butanol or glycol), ketones (such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone), esters (including fats and oils) and polyethers, unsubstituted and substituted amines, amides (such as dimethylformamide), lactams (such as N-alkylpyrrolidones) and lactones, sulfones and sulfoxides (such as dimethyl sulfoxide). The carrier may also be a liquefied gaseous excipient, that is, a liquid that is gaseous at standard temperature and pressure, such as aerosol propellant gases such as halocarbons, butane, propane, nitrogen, and carbon dioxide.

The amount of carrier is usually 1 to 99.99%, preferably 5 to 99.9%, more preferably 10 to 99.5% and most preferably 20 to 99% by weight of the composition.

The surfactant may be an ionic (cationic or anionic) or non-ionic surfactant such as an ionic or non-ionic emulsifier(s), foaming agent(s), dispersant(s), wetting agent(s), 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 naphthalene sulfonic acid, polycondensates of ethylene and/or propylene oxide with fatty alcohols, fatty acids, or fatty amines (esters of polyoxyethylene and fatty acids). acids, ethers of polyoxyethylene and fatty alcohols, e.g. alkylaryl ethers of polyglycols), substituted phenols (preferably alkylphenols or arylphenols), salts of sulfosuccinic acid esters, taurine derivatives (preferably alkyl taurates), phosphoric acid esters of polyethoxylated alcohols or phenols , fatty esters of polyols and derivatives of compounds containing sulfates, sulfonates, phosphates (eg alkyl sulfonates, alkyl sulfates, arylsulfonates) and protein hydrolysates, lignosulfite waste liquors and methylcellulose. A surfactant is usually used when the compounds of the invention and/or the carrier are insoluble in water and the application is carried out with water. Then the amount of surfactants usually varies from 5 to 40% by weight of the composition.

Other examples of suitable excipients include water repellents, drying agents, binders (adhesive, tackifier, fixing agent such as carboxymethylcellulose, 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 cephalins and lecithins and synthetic phospholipids, polyvinylpyrrolidone and tylose), thickeners, stabilizers (for example, low temperature stabilizers, preservatives, antioxidants, light stabilizers or other agents that improve chemical and/or physical stability), colorants or pigments (such as inorganic pigments such as iron oxide, titanium oxide and Prussian blue; organic dyes such as alizarin, azo and metal phthalocyanine dyes), defoamers (such as silicone defoamers and magnesium stearate), preservatives (such as dichlorophene and benzyl hemiformal). alcohol), secondary thickeners (cellulose derivatives, acrylic acid derivatives, xanthan, modified clays and fumed silica), adhesives, gibberellins and processing aids, mineral and vegetable oils, fragrances, waxes, nutrients (including trace elements such as salts iron, manganese, boron, copper, cobalt, molybdenum and zinc), protective colloids, thixotropic agents, penetrating agents, binding agents and complexing agents.

The choice of excipients depends on the intended use of the compound according to the invention and/or on the physical properties. In addition, excipients can be selected to impart specific properties (technical, physical and/or biological properties) to compositions or forms of application prepared from them. The choice of excipients may allow the compositions to be tailored to specific needs.

The composition according to the invention may be in any conventional form such as solutions (e.g. aqueous solutions), emulsions, wettable powders, aqueous and oily suspensions, powders, powders, pastes, soluble powders, soluble granules, spreading granules, suspoemulsion concentrates , natural or synthetic products impregnated with the compound(s) according to the invention, fertilizers, as well as microcapsules in polymeric substances. The compound(s) according to the invention may be present in suspended, emulsified or dissolved form.

The composition according to the invention can be provided to the end user as a ready-to-use composition, ie these compositions can be directly applied to plants or seeds using a suitable device such as a spray or dusting device. Alternatively, the compositions may be provided to the end user in the form of concentrates which must be diluted, preferably with water, before use.

The composition according to the invention can be prepared by conventional methods, for example, by mixing the compound (compounds) according to the invention with one or more suitable excipients, such as those disclosed herein above.

The composition according to the invention usually 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(s) according to the invention. It is possible that the composition contains two or more compounds according to the invention. In this case, the specified ranges refer to the total number of compounds according to the present invention.

Mixes/Combinations

The compound(s) and composition according to the invention may be mixed with other active ingredients such as fungicides, bactericides, acaricides, nematocides, insecticides, herbicides, fertilizers, growth regulators, safeners and/or chemical signal agents. This may expand the spectrum of activity or prevent the development of resistance. Examples of known fungicides, insecticides, acaricides, nematicides and bactericides are disclosed in the Pesticide Manual, ^17th Edition.

Examples of particularly preferred fungicides that can be mixed with the compound(s) and composition of the invention are:

1) Ergosterol biosynthesis inhibitors, e.g. (1.001) cyproconazole, (1.002) difenoconazole, (1.003) epoxiconazole, (1.004) fenhexamide, (1.005) fenpropidine, (1.006) fenpropimorph, (1.007) fenpyrazamine, (1.008) fluquincone azole, (1.009 ) flutriafol, (1.010) imazalil, (1.011) imazalyl sulfate, (1.012) ipconazole, (1.013) metconazole, (1.014) myclobutanil, (1.015) paclobutrazol, (1.016) prochloraz, (1.017) propiconazole, (1.018) anti okonazol, (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, (1.031) (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)oxiran-2-yl]methyl}-1H-1,2,4-triazol-5-ylthiocyanate, (1.040) 1-{[rel.(2R ,3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-1H-1,2,4-triazol-5-ylthiocyanate, (1.041) 1-{ [rel.(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-1H-1,2,4-triazol-5-ylthiocyanate 1.042) 2-[(2R,4R,5R)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylheptan-4-yl]-2,4-dihydro-3H-1, 2,4-triazol-3-thione, (1.043) 2-[(2R,4R,5S)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylheptan-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-trimethylheptan-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-trimethylheptan-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-trimethylheptan-4-yl]-2,4-dihydro-3H-1,2,4-triazol- 3-thione, (1.047) 2-[(2S,4R,5S)-1-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylheptan-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-trimethyl -heptan-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-trimethylheptan-4-yl]-2,4-dihydro-3H-1,2,4-triazole-3-thione, (1.050) 2-[1-(2, 4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylheptan-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-triazol-3-thione, (1.057) 2-{[rel.(2R,3R)-3-(2-chlorophenyl) -2-(2,4-difluorophenyl)oxiran-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)oxiran-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)oxiran-2-yl]methyl}-1H-1,2,4-triazole, (1.061) 5-(allylsulfanyl)-1- {[rel.(2R,3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-1H-1,2,4-triazole, (1.062) 5 -(allylsulfanyl)-1-{[rel(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-1Н-1,2,4- triazole, (1.063) N'-(2,5-dimethyl-4-{[3-(1,1,2,2-tetrafluoroethoxy)phenyl]sulfanyl}phenyl)-N-ethyl-N-methylimidoformamide, (1.064) N'-(2,5-dimethyl-4-{[3-(2,2,2-trifluoroethoxy)phenyl]sulfanyl}phenyl)-N-ethyl-N-methylimidoformamide, (1.065) N'-(2.5 -dimethyl-4-{[3-(2,2,3,3-tetrafluoropropoxy)phenyl]sulfanyl}phenyl)-N-ethyl-N-methylimidoformamide, (1.066) N'-(2,5-dimethyl-4- {[3-(pentafluoroethoxy)phenyl]sulfanyl}phenyl)-N-ethyl-N-methylimidoformamide, (1.067) N'-(2,5-dimethyl-4-{3-[(1,1,2,2- tetrafluoroethyl)sulfanyl]phenoxy}phenyl)-N-ethyl-N-methylimidoformamide, (1.068) N'-(2,5-dimethyl-4-{3-[(2,2,2-trifluoroethyl)sulfanyl]phenoxy}phenyl )-N-ethyl-N-methylimidoformamide, (1.069) N'-(2,5-dimethyl-4-{3-[(2,2,3,3-tetrafluoropropyl)sulfanyl]phenoxy}phenyl)-N-ethyl -N-methylimidoformamide, (1.070) N'-(2,5-dimethyl-4-{3-[(pentafluoroethyl)sulfanyl]phenoxy}phenyl)-N-ethyl-N-methylimidoformamide, (1.071) N'-(2 ,5-dimethyl-4-phenoxyphenyl)-N-ethyl-N-methylimidoformamide, (1.072) N'-(4-{[3-(difluoromethoxy)phenyl]sulfanyl}-2,5-dimethylphenyl)-N-ethyl- N-methylimidoformamide, (1.073) N'-(4-{3-[(difluoromethyl)sulfanyl]phenoxy}-2,5-dimethylphenyl)-N-ethyl-N-methylimidoformamide, (1.074) N'-[5-bromo -6-(2,3-dihydro-1H-inden-2-yloxy)-2-methylpyridin-3-yl]-N-ethyl-N-methylimidoformamide, (1.075) N'-{4-[(4.5 -dichloro-1,3-thiazol-2-yl)oxy]-2,5-dimethylphenyl}-N-ethyl-N-methylimidoformamide, (1.076) N'-{5-bromo-6-[(1R)-1 -(3,5-difluorophenyl)ethoxy]-2-methylpyridin-3-yl}-N-ethyl-N-methylimidoformamide, (1.077) N'-{5-bromo-6-[(1S)-1-(3 ,5-difluorophenyl)ethoxy]-2-methylpyridin-3-yl}-N-ethyl-N-methylimidoformamide, (1.078) N'-{5-bromo-6-[(cis-4-isopropylcyclohexyl)oxy]-2 -methylpyridin-3-yl}-N-ethyl-N-methylimidoformamide, (1.079) N'-{5-bromo-6-[(trans-4-isopropylcyclohexyl)oxy]-2-methylpyridin-3-yl}-N -ethyl-N-methylimidoformamide, (1.080) N'-{5-bromo-6-[1-(3,5-difluorophenyl)ethoxy]-2-methylpyridin-3-yl}-N-ethyl-N-methylimidoformamide, (1.081) Ipfentrifluconazole.

2) Respiratory chain inhibitors in complex I or II, e.g. (2.001) benzovindiflupyr, (2.002) bixafen, (2.003) boscalide, (2.004) carboxin, (2.005) fluopyram, (2.006) flutolanil, (2.007) fluxapiroxade, (2.008) ) furametpyr, (2.009) isofetamide, (2.010) isopyrazam (anti-epimer enantiomer 1R,4S,9S), (2.011) isopyrazam (anti-epimer enantiomer 1S,4R,9R), (2.012) isopyrazam (anti-epimer racemate 1 RS,4SR,9SR), (2.013) isopyrase (mixture of syn-epimer racemate 1RS,4SR,9RS and anti-epimer racemate 1 RS,4SR,9SR), (2.014) isopyrase (syn-epimer enantiomer 1R,4S,9R) , (2.015) isopyrazam (syn epimeric enantiomer 1S,4R,9S), (2.016) isopyrazam (syn epimeric racemate 1 RS,4SR,9RS), (2.017) penflufen, (2.018) penthiopyrad, (2.019) pidiflumethofen, 2.020) pyraziflumide, (2.021) sedaxan, (2.022) 1,3-dimethyl-N-(1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl)-1H-pyrazol-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, (2.028) 3-(difluoromethyl)-1-methyl-N-[(3R)-1,1,3-trimethyl-2, 3-dihydro-1H-inden-4-yl]-1H-pyrazole-4-carboxamide, (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-methanonaphthalen-5-yl]-3-(difluoromethyl)-1-methyl-1H-pyrazole -4-carboxamide, (2.040) N-[(1S,4R)-9-(dichloromethylene)-1,2,3,4-tetrahydro-1,4-methanonaphthalen-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-carbothioamide, (2.049) M-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) pyrapropoin.

3) Respiratory chain inhibitors in complex III, e.g. (3.001) amethoctradin, (3.002) amisulbrom, (3.003) azoxystrobin, (3.004) cumethoxystrobin, (3.005) cumoxystrobin, (3.006) cyazofamide, (3.007) dimoxystrobin, (3.008) enoxa strobin , (3.009) famoxadone, (3.010) fenamidone, (3.011) fluphenoxystrobin, (3.012) fluoxastrobin, (3.013) kresoxim-methyl, (3.014) methominostrobin, (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- phenylvinyl]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) (3S,6S,7R ,8R)-8-benzyl-3-[({3-[(isobutyryloxy)methoxy]-4-methoxypyridin-2-yl}carbonyl)amino]-6-methyl-4,9-dioxo-1,5-dioxonane -7-yl-2-methylpropanoate, (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, (3.029) methyl{5- [3-(2,4-dimethylphenyl)-1H-pyrazol-1-yl]-2-methylbenzyl}carbamate, (3.030) methyltetraprol, (3.031) florylpicoxamide.

4) Inhibitors of mitosis and cell division, e.g. (4.001) carbendazim, (4.002) dietofencarb, (4.003) ethaboxam, (4.004) fluopicolide, (4.005) pencycuron, (4.006) thiabendazole, (4.007) thiophanate-methyl, (4.008) zoxamide, (4.009) 3-chloro-4-(2,6-difluorophenyl)-6-methyl-5-phenylpyridazine, (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-pyrazole-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-pyrazole-5-amine, (4.015) 4-(2-bromo-4-fluorophenyl)-N-(2-chloro-6-fluorophenyl)-1,3-dimethyl-1H-pyrazole-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-pyrazole-5-amine, (4.018) 4-(2-chloro-4-fluorophenyl)-N-(2,6-difluorophenyl)-1 ,3-dimethyl-1H-pyrazole-5-amine, (4.019) 4-(2-chloro-4-fluorophenyl)-N-(2-chloro-6-fluorophenyl)-1,3-dimethyl-1H-pyrazole- 5-amine, (4.020) 4-(2-chloro-4-fluoro-phenyl)-N-(2-chlorophenyl)-1,3-dimethyl-1H-pyrazole-5-amine, (4.021) 4-(2 -chloro-4-fluorophenyl)-N-(2-fluorophenyl)-1,3-dimethyl-1H-pyrazole-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-pyrazole-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-pyrazole-5-amine.

5) Compounds with multilateral action, for example, (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 sulfate (2+), (5.010) dithianone, (5.011) dodin, (5.012) folpet, (5.013) mancozeb, (5.014) maneb, (5.015) metiram, (5.016) metiram zinc , (5.017) oxin-copper, (5.018) propineb, (5.019) sulfur and sulfur preparations, including calcium polysulfide, (5.020) thiram, (5.021) cineb, (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.

6) Compounds that induce host defense, eg (6.001) acibenzolar-S-methyl, (6.002) isothianil, (6.003) probenazole, (6.004) thiadinyl.

7) Inhibitors of amino acid and/or protein biosynthesis, e.g. (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.

8) ATP production inhibitors, eg (8.001) silthiopham.

9) Cell wall synthesis inhibitors e.g. -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.

10) Lipid and membrane synthesis inhibitors, eg (10.001) propamocarb, (10.002) propamocarb hydrochloride, (10.003) tolclofos-methyl.

11) Inhibitors of melanin biosynthesis, eg (11.001) tricyclazole, (11.002) 2,2,2-trifluoroethyl{3-methyl-1-[(4-methylbenzoyl)amino]butan-2-yl}carbamate.

12) Inhibitors of nucleic acid synthesis, for example, (12.001) benalaxyl, (12.002) benalaxyl-M (chiralaxyl), (12.003) metalaxyl, (12.004) metalaxyl-M (mefenoxam).

13) Signal transduction inhibitors e.g.

14) Compounds acting as uncouplers, eg (14.001) fluazinam, (14.002) meptyldinocap.

15) Other compounds, e.g. (15.001) abscisic acid, (15.002) benthiazole, (15.003) betoxazine, (15.004) capsimycin, (15.005) carvone, (15.006) quinomethionate, (15.007) kufraneb, (15.008) cyflufenamid , (15.009 ) cymoxanil, (15.010) cyprosulfamide, (15.011) fluthianil, (15.012) fosetyl-aluminum, (15.013) fosetyl-calcium, (15.014) fosetyl-sodium, (15.015) methylisothiocyanate, (15.016) metrafenone, (15.01) 7) mildiomycin, ( 15.018) natamycin, (15.019) nickel dimethyldithiocarbamate, (15.020) nitrotalisopropyl, (15.021) oxamocarb, (15.022) oxathiapiproline, (15.023) oxyfentiin, (15.024) pentachlorophenol and its salts, (15.025) phosphoric acid and its salts, (15.025) 15.026) propamocarb-fosetilate, (15.027) pyriophenone (chlazaphenone), (15.028) tebufloquin, (15.029) teclophthalam, (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) dipimethitrone, (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-chlorophenylmethanesulfonate, (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-chlorophenylmethanesulfonate, (15.041) ipflufenoquin, (15.042) 2-{2-fluoro-6-[(8-fluoro-2-methylquinolin-3-yl)oxy] phenyl}propan-2-ol, (15.043) 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}-3-chlorophenylmethanesulfonate, (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 }phenylmethanesulfonate, (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-thiadiazol-2-thiol, (15.051) 5-chloro-N'-phenyl-N'-(prop-2-yn-1-yl)thiophen- 2-sulfonohydrazide, (15.052) 5-fluoro-2-[(4-fluorobenzyl)oxy]pyrimidine-4-amine, (15.053) 5-fluoro-2-[(4-methylbenzyl)oxy]pyrimidine-4-amine, (15.054) 9-fluoro-2,2-dimethyl-5-(quinolin-3-yl)-2,3-dihydro-1,4-benzoxazepine, (15.055) but-3-yn-1-yl{6- [({[(2)-(1-methyl-1H-tetrazol-5-yl) (phenyl)methylene]amino}oxy)methyl]pyridin-2-yl}carbamate, (15.056) ethyl-(2Z)-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) quinoline-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.

All named participants in mixtures from classes (1) to (15), as described herein above, may be present in the form of the free compound and/or, if their functional groups allow it, its agriculturally acceptable salt.

In some embodiments, the combinations of compounds contain the following components:

II.1 (eg II.01) and the second component is a fungicide selected from groups 1 to 15 as defined herein. For example, the combination (II.01) + (1.001) corresponds to the combination containing compound 11.01 in Table 11.1 and cyproconazole (1.001).

In some other embodiments, the compound combinations correspond to the combinations described above, in which the compound (11.01) is replaced by any one of the compounds listed in Table 11.1.

Compounds of formula (II) and a fungicide selected from groups (1) to (15) may be present in a weight ratio ranging from 100:1 to 1:100 (compound of formula (II): fungicide selected from group c (1 ) according to (15)), or varying from 50:1 to 1:50, or varying from 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, from 35:1 to 1:35, from 30:1 to 1:30, from 25:1 to 1:25, from 15:1 to 1:15, from 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.

Another fungicide selected from groups 1 to 15, as defined herein, may be added to compound combinations.

The compound(s) and composition of the invention may also be combined with one or more biological control agents.

Examples of biological control agents that can be combined with the compound(s) and composition of the invention are:

(A) Antibacterial agents selected from the group:

(A1) bacteria such as (A1.1) Bacillus subtilis, in particular strain QST713/AQ713 (available as SERENADE OPTI or SERENADE ASO from Bayer CropScience LP, USA, NRRL Accession B21661 and described in US Patent No. US 6,060,051 ); (A1.2) Bacillus amyloliquefaclens, in particular strain D747 (available as Double Nickel™ from Certis, USA, FERM accession number BP-8234 and disclosed in US Pat. No. US 7,094,592); (A1.3) Bacillus pumilus, in particular strain BU F-33 (registration number NRRL 50185); (A1.4) Bacillus subtilis var, amyloliquefaciens, strain FZB24 (available as Taegro® from Novozymes, USA); (A1.5) Paenibacillus sp. strain of NRRL accession B-50972 or NRRL accession B-67129 and described in International Patent Publication WO 2016/154297; And

(A2) fungi such as (A2.1) Aureobasidium pullulans, in particular blastospores of strain DSM14940; (A2.2) blastospores of Aureobasidium pullulans strain DSM 14941; (A2.3) Aureobasidium pullulans, in particular mixtures of blastospores of strains DSM14940 and DSM14941;

(B) Fungicides selected from the group:

(B1) bacteria, for example (B1.1) Bacillus subtilis, in particular strain QST713/AQ713 (available as SERENADE OPTI or SERENADE ASO from Bayer CropScience LP, USA, NRRL Accession B21661 and described in US Pat. No. 6,060,051); (B1.2) Bacillus pumilus, in particular strain QST2808 (available as SONATA® from Bayer CropScience LP, USA, NRRL Accession B-30087 and described in US Pat. No. 6,245,551); (B1.3) Bacillus pumilus, in particular strain GB34 (available as Yield Shield® from Bayer AG, Germany); (B1.4) Bacillus pumilus, in particular strain BU F-33 (registration number NRRL 50185); (B1.5) Bacillus amyloliquefaciens, in particular strain D747 (available as Double Nickel™ from Certis, USA, FERM accession number BP-8234 and disclosed in US Pat. No. 7,094,592); (B1.6) Bacillus subtilis Y1336 (available as BIOBAC® WP from Bion-Tech, Taiwan, registered as a biological fungicide in Taiwan under registration numbers 4764, 5454, 5096 and 5277); (B1.7) Bacillus amyloliquefaciens strain MBI 600 (available as SUBTILEX from BASF SE); (B1.8) Bacillus subtilis strain GB03 (available as Kodiak® from Bayer AG, DE); (B1.9) Bacillus subtilis var, amyloliquefaciens, strain FZB24 (available from Novozymes Biologicals Inc., Salem, VA or Syngenta Crop Protection, LLC, Greensboro, NC, as TAEGRO® or TAEGRO® ECO fungicide (EPA registration number 70127- 5); (B1.10) Bacillus mycoides, isolate J (available as BmJ TGAI or WG from Certis USA); (B1.11) Bacillus licheniformis, in particular strain SB3086 (available as EcoGuard TM Biofungicide and Green Releaf from Novozymes) ; (B1.12) PaenibaciHus sp., strain NRRL accession B-50972 or NRRL accession B-67129 and described in International Patent Publication WO 2016/154297.

In some embodiments, the biological control agent is a strain of Bacillus subtilis or Bacillus amyloliquefaciens that produces a fengycin or plipastatin type compound, an iturin type compound, and/or a surfactin type compound. For available research, see the following review article: "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 as SERENADE OPTI or SERENADE ASO from Bayer CropScience LP, USA, NRRL B21661 and described in US Pat. No. 6,060,051), Bacillus amyloliquefaciens strain D747 (available as Double Nickel ™ from Certis, USA, having the registration number FERM BP-8234 and disclosed in US patent US 7,094,592); Bacillus subtilis MBI600 (available as SUBTILEX® from Becker Underwood, US Environmental Protection Agency (EPA) registration number 71840-8); Bacillus subtilis Y1336 (available as BIOBAC® WP from Bion-Tech, Taiwan, registered as a biological fungicide in Taiwan under registration numbers 4764, 5454, 5096 and 5277); Bacillus amyloliquefaciens, in particular strain FZB42 (available as RHIZOVITAL® from ABiTEP, Germany); and Bacillus subtilis var. amyloliquefaciens FZB24 (available from Novozymes Biologicals Inc., Salem, VA or Syngenta Crop Protection, LLC, Greensboro, NC as TAEGRO® or TAEGRO® ECO fungicide (EPA accession number 70127-5); and

(B2) fungi, eg: (B2.1) Coniothyhum minitans, in particular strain CON/M/91-8 (accession number DSM-9660; eg Contans® from Bayer); (B2.2) Metschnikowia fructicola, in particular strain NRRL Y-30752 (eg Shemer®); (B2.3) Microsphaeropsis ochracea (eg Microx® from Prophyta); (B2.5) Trichoderma spp., including Thchoderma atroviride, strain SC1 described in international application PCT/IT2008/000196); (B2.6) Trichoderma harzianum rifai strain KRL-AG2 (also known as strain T-22./ATCC 208479, eg PLANTSHIELD T-22G, Rootshield® and TurfShield from BioWorks, USA); (B2.14) Gliocladium roseum, strain 321U from W.F. Stoneman Company LLC; (B2.35) Talaromyces Havus strain V117b; (B2.36) Trichoderma asperellum strain ICC 012 from Isagro; (B2.37) Trichoderma asperellum strain SKT-1 (eg ECO-HOPE® from Kumiai Chemical Industry); (B2.38) Trichoderma atroviride strain CNCM 1-1237 (eg Esquive® WP from Agrauxine, FR); (B2.39) Trichoderma atroviride, strain no. V08/002387; (B2.40) Trichoderma atroviride strain NMI no. V08/002388; (B2.41) Trichoderma atroviride strain NMI no. V08/002389; (B2.42) Trichoderma atroviride strain NMI no. V08/002390; (B2.43) Trichoderma atroviride strain LC52 (eg Tenet from Agrimm Technologies Limited); (B2.44) Trichoderma atrovihde strain ATCC 20476 (IMI 206040); (B2.45) Trichoderma atroviride strain T11 (IMI352941/CECT20498); (B2.46) Trichoderma harmatum; (B2.47) Trichoderma harzianum; (B2.48) Trichoderma harzianum rifai T39 (eg Trichodex® from Makhteshim, USA); (B2.49) Trichoderma harzianum, in particular strain KD (eg Trichoplus from Biological Control Products, SA (purchased by Becker Underwood)); (B2.50) Trichoderma harzianum strain ITEM 908 (eg Trianum-P from Koppert); (B2.51) Trichoderma harzianum strain TH35 (eg Root-Pro from Mycontrol); (B2.52) Trichoderma virens (also known as Gliocladium virens), in particular strain GL-21 (eg SoilGard 12G from Certis, USA); (B2.53) Trichoderma viride strain TV1 (eg Trianum-P from Koppert); (B2.54) Ampeiomyces quisqualis, in particular strain AQ 10 (eg AQ 10® from IntrachemBio, Italy); (Q2.56) Aureobasidium pullulans, in particular blastospores of strain DSM14940; (Q2.57) Aureobasidium pullulans, in particular blastospores of strain DSM 14941; (B2.58) Aureobasidium pullulans, in particular blastospore mixtures of strains DSM14940 and DSM 14941 (eg Botector® from bio-ferm, CH); (B2.64) Cladosporium cladosporioides strain H39 (Stichting Dienst Landbouwkundig Onderzoek); (B2.69) Gliocladium catenulatum (synonym: Clonostachys rosea f. catenulate), strain J1446 (eg Prestop® from AgBio Inc. and also, for example, Primastop® from Kemira Agro Oy); (B2.70) Lecanicillium lecanii (formerly known as Verticillium lecanii) conidia strain KV01 (eg Vertalec® from 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 (IMI CC 392151 CABI, e.g. BioDerma from AGROBIOSOL DE MEXICO, S.A. DE C.V.); (B2.79) Trichoderma harzianum strain DB 103 (eg T-Gro 7456 from Dagutat Biolab); (B2.80) Trichoderma polysporum strain IMI 206039 (eg Binab TF WP from BINAB Bio-Innovation AB, Sweden); (B2.81) Trichoderma stromaticum (eg Tricovab from Ceplac, Brazil); (B2.83) Uiocladium oudemansii, in particular strain HRU3 (eg Botry-Zen® from Botry-Zen Ltd, NZ); (B2.84) Verticillium albo-atrum (formerly V, dahliae), strain WCS850 (CBS 276.92; eg Dutch Trig from Tree Care Innovations); (B2.86) Verticillium chlamydospohum; (B2.87) a mixture of Trichoderma asperellum strain ICC 012 and Trichoderma gamsii strain ICC 080 (product known for example as VU-TAM™ from Bayer CropScience LP, USA).

Other examples of biological control agents that can be combined with the compound(s) and composition of the invention are:

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

fungi and yeasts selected from the group consisting of Beauveria bassiana, in particular strain ATCC 74040, Lecanicillium spp., in particular strain HRO LEC 12, Metarhizium anisopliae, in particular strain F52 (DSM3884 or ATCC 90448), Paecilomyces fumosoroseus ( currently: Isaaria fumosoroseus), in particular strain IFPC 200613 or strain Arorca 97 (accession number ATCC 20874), and Paecilomyces lilacinus, in particular P. lilacinus strain 251 (AGAL 89/030550);

viruses selected from the group consisting of granulosa virus (GV) Adoxophyes orapa (net-roller), granulosa virus (GV) Cydia pomonella (codling moth), nuclear polyhedrosis virus (NPV) Helicoverpa armigera (cotton bollworm), Spodoptera exigua (small cutworm ) mNPV, Spodoptera frugiperda (Little armyworm) mNPV and Spodoptera littoralis (African cotton bollworm) NPV;

bacteria and fungi which can be added as an "inoculant" to plants, plant parts or plant organs and which, due to their specific properties, promote plant growth and health.

Examples are: Agrobactehum spp., Azorhizobium caulinodans, AzospirHlum spp., Azotobacter spp., Bradyrhizobium spp., Burkholderia spp. Laccaria spp., Lactobacillus buchneh, Paraglomus spp., Pisolithus tinctorus, Pseudomonas spp., Rhizobium spp., in particular Rhizobium trifolii, Rhizopogon spp., Scleroderma spp., Suillus spp. and Streptomyces spp.

plant extracts and products formed by microorganisms, including proteins and secondary metabolites that can be used as biological control agents, such as Allium sativum, Artemisia absinthium, azadirachtin, Biokeeper WP, Cassia nigricans, Celastrus angulatus, Chenopodium anthelminticum, chitin, Armor-Zen , Dryopteris filix-mas, Equisetum arvense, Fortune Aza, Fungastop, Heads Up (Chenopodium quinoa saponin extract), Pirethrum/Pirethrins, Quassia amara, Quercus, Quillaja, Regalia, "Requiem™ Insecticide", rotenone, ryania/ryanodine, Symphytum officinale , Tanacetum vulgare, thymol, Triact 70, TriCon, Tropaeulum majus, Urtica dioica, veratrin, Viscum album, Brassicaceae extract, in particular oilseed rape powder or mustard powder.

Examples of insecticides, acaricides and nematicides, respectively, which can be mixed with the compound(s) and composition according to the invention are:

(1) Acetylcholinesterase (AChE) inhibitors such as, for example, carbamates, e.g. omil , metolcarb, oxamyl, pirimicarb, propoxur, thiodicarb, thiophanox, triazamate, trimetacarb, CMS and xylylcarb; or organic phosphates, e.g. acephate, azamethifos, azinphos-ethyl, azafinphos-methyl, cadusafos, chlorethoxyphos, chlorfenvinphos, chlormephos, chlorpyrifos-methyl, coumaphos, cyanophos, demeton-B-methyl, diazinon, dichlorvos/DDVP, dicrotophos, dimethoate, dimethylvinphos, disulfotone, EPN, ethion, etoprofos, famfur, fenamiphos, fenitrothion, fenthion, fostiazate, heptenophos, isofenphos, isopropyl-O-(methoxyaminothiophosphoryl) salicylate, isoxathion, malathion, mecarbam, methamidophos, metidiathion, mevinphos, monocrotophos, naled, omethoate , oxydemeton-methyl, parathion-methyl, phentoate, phorate, fosalone, phosmet, phosphamidon, phoxim, pyrimiphos-methyl, profenophos, propetamphos, prothiophos, pyraclophos, pyridafenthion, quinalphos, sulfotep, tebupyrimphos, temephos, terbufos, tetrachlorvinphos, thiometon, triaz ofos , trichlorfon and vamidothione.

(2) GABA-regulated chloride ion channel antagonists such as, for example, cyclodiene organochlorines, eg chlordan and endosulfan, or phenylpyrazoles (fiproles), eg ethiprol and fipronil.

(3) Sodium channel modulators such as, for example, pyrethroids, e.g. -cyfluthrin, cyhalothrin, lambda-cyhalothrin, gamma-cyhalothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, theta-cypermethrin, zeta-cypermethrin, cyfenotrin [(1R)-trans-isomer], deltamethrin, empentrin [(EZ)- (1R)-isomer], esfenvalerate, etofenprox, fenpropatrin, fenpyrythrin, fenvalerate, flucitrinate, flumethrin, tau-fluvalinate, halfenprox, imiprotrin, cadetrin, momfloorothrin, permethrin, phenothrin [(1R)-trans-isomer)], pralletrin, pyrethrin (feverfew), resmethrin, silafluofen, tefluthrin, tetramethrin, tetramethrin [(1R)-isomer], tralometrin and transfluthrin or DDT or methoxychlor.

(4) Nicotinic acetylcholine receptor (nAChR) competitive modulators such as, for example, neonicotinoids such as acetampiride, clothianidin, dinotefuran, imidacloprid, nitenpyram, thiacloprid and thiamethoxam, or nicotine or sulfoxaflor or flupyradifuron.

(5) Allosteric modulators of the nicotinic acetylcholine receptor (nAChR), such as, for example, spinosyns, eg spinetoram and spinosad.

(6) Allosteric modulators of glutamate-gated chloride channels (GIuCI) such as, for example, avermectins/milbemycins, eg abamectin, emamectin benzoate, lepimectin and milbemectin.

(7) Juvenile hormone mimics, eg juvenile hormone analogs, eg hydroprene, kinoprene and methoprene or fenoxycarb or pyriproxyfen.

(8) Other non-specific (multi-site) inhibitors such as, for example, alkyl halides, eg methyl bromide and other alkyl halides; or chloropicrin, or sulfuryl fluoride, or borax, or emetic stone, or methyl isocyanate generators, eg diazomethimetam.

(9) Chordotonal organ modulators such as, for example, pymetrozine or flonicamid.

(10) Mite growth inhibitors such as, for example, clofentezin, hexythiazox and difluvidazine or ethoxazole.

(11) Microbial disruptors of the lining of the alimentary canal of insects, such as, for example, Bacillus thuhngiensis subsp. israelensis, Bacillus sphaericus, Bacillus thuringiensis subsp. aizawai, Bacillus thuhngiensis subsp. kurstaki, Bacillus thuhngiensis subsp. tenebrionis, and plant proteins B.t., e.g., Cry1Ab, Cry1A c, Cry1Fa, Cry2Ab, mCry3A, Cry3Ab, Cry3Bb, Cry34/35Ab1.

(12) Inhibitors of mitochondrial ATP synthase such as ATP disintegrators such as for example diafenthiuron or organotin compounds such as azocyclotin, cyhexatin and fenbutatin oxide or propargit or tetradifon.

(13) Oxidative phosphorylation interrupters acting by interrupting the proton gradient, such as, for example, chlorfenapyr and DNOC and sulfuramide.

(14) Nicotinic acetylcholine receptor channel blockers such as, for example, bensultap, cartap hydrochloride, thiocylam and sodium thiosultap.

(15) Type 0 chitin biosynthesis inhibitors such as, for example, bistrifluron, chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, teflubenzuron or triflumuron.

(16) Inhibitors of chitin biosynthesis type 1, such as, for example, buprofezin.

(17) Anti-moulting agents (in particular for Diptera, i.e. Diptera), such as, for example, cyromazine.

(18) Ecdysone receptor agonists such as, for example, chromafenoside, halofenoside, methoxyfenoside and tebufenoside.

(19) Octopamine receptor agonists such as, for example, amitraz.

(20) Mitochondrial complex III electron transfer inhibitors such as, for example, hydramethylnon; acequinocil; fluacripyrim.

(21) Mitochondrial complex I electron transfer inhibitors, such as from the group of ECM inhibitor acaricides, eg phenazquin, fenpyroximate, pyrimidifen, pyridaben, tebufenpyrad, tolfenpyrad; or rotenone (derris).

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

(23) Acetyl coenzyme A carboxylase inhibitors, such as, for example, tetronic and tetramic acid derivatives, for example, spirodiclofen, spiromesifen and spirotetramat.

(24) Mitochondrial complex IV electron transport inhibitors such as, for example, phosphines, such as aluminum phosphide, calcium phosphide, phosphine and zinc phosphide, or cyanides, such as calcium cyanide, potassium cyanide and sodium cyanide.

(25) Mitochondrial complex II electron transfer inhibitors, such as, for example, beta-ketonitrile derivatives, such as cyenopyraphene and cyflumethophen, and carboxanilides, such as, for example, piflubumide.

(28) Ryanodine receptor modulators such as, for example, diamides, such as chlorantraniliprole, cyantraniliprole and flubendiamide,

other active compounds such as, for example, afidopyropene, afoxolaner, azadirachtin, bentclothiaz, benzoximate, bifenazat, broflanilide, bromopropylate, quinomethionate, chloropralletrin, cryolite, cyclaniliprol, cycloxapride, cyhalodiamide, dichloromesothiaz, dicofol, epsilon-methofluthrin, epsilon-momfluthrin, flomethoquin , fluazaindolizine, fluensulfone, flufenerim, flufenoxystrobin, flufiprol, fluhexafon, fluopyram, fluralaner, fluxametamide, flufenoside, guadipyr, heptafluthrin, imidaclotiz, iprodione, kappa-bifenthrin, kappa-tefluthrin, lotilaner, meperfluthrin, paichong ding, pyridalil, pyrifluquinasone, pyriminostrobin, spirobudiclofen , tetramethylfluthrin, tetraniliprole, tetrachloranthraniliprole, tigolaner, thioxazafen, thiofluoximate, triflumesopyrim, and iodomethane; in addition, preparations based on Bacillus firmus (I-1582, BioNeem, Votivo), as well as 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 WO 2006/043635) (CAS 885026-50-6), {1'-[(2E)-3- (4-chlorophenyl)prop-2-en-1-yl]-5-fluorospiro[indol-3,4'-piperidin]-1(2H)-yl}(2-chloropyridin-4-yl)methanone (known from WO 2003/106457) (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 WO 2006/003494) (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) (CAS 1225292-17-0), 3-(4-chloro-2,6 -dimethylphenyl)-8-methoxy-2-oxo-1,8-diazaspiro[4.5]dec-3-en-4-ylethyl carbonate (known from EP 2647626) (CAS 1440516-42-6), 4-(but -2-yn-1-yloxy)-6-(3,5-dimethylpiperidin-1-yl)-5-fluoropyrimidine (known from WO 2004/099160) (CAS 792914-58-0), PF1364 (known from Japanese patent JP 2010/018586) (CAS 1204776-60-2), N-[(2E)-1-[(6-chloropyridin-3-yl)methyl]pyridin-2(1H)-ylidene]-2.2 ,2-trifluoroacetamide (known from international application WO 2012/029672) (CAS 1363400-41-2), (3E)-3-[1-[(6-chloro-3-pyridyl)methyl]-2-pyridylidene]- 1,1,1-trifluoropropan-2-one (known from WO 2013/144213) (CAS 1461743-15-6), N-[3-(benzylcarbamoyl)-4-chlorophenyl]-1-methyl-3- (pentafluoroethyl)-4-(trifluoromethyl)-1H-pyrazole-5-carboxamide (known from WO 2010/051926) (CAS 1226889-14-0), 5-bromo-4-chloro-N-[4-chloro -2-methyl-6-(methylcarbamoyl)phenyl]-2-(3-chloro-2-pyridyl)pyrazole-3-carboxamide (known from Chinese patent CN 103232431) (CAS 1449220-44-3), 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-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 international applications WO 2013/162715 A2, WO 2013/162716 A2, US patent 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 Chinese patent CN 101337937 A) (CAS 1105672-77-2), 3-bromo-N-[4-chloro-2-methyl-6-[(methylamino)thioxomethyl]phenyl]-1-(3-chloro-2-pyridinyl )-1H-pyrazole-5-carboxamide (Liudaibenjiaxuanan, known from Chinese patent 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 international application 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-yl)oxy]phenoxy]propoxy]-2-methoxy-6-(trifluoromethyl)pyrimidine (known from Chinese patent CN 101337940 A) (CAS 1108184-52-6); (2E)- and 2(Z)-2-[2-(4-cyanophenyl)-1-[3-(trifluoromethyl)phenyl]ethylidene]-N-[4-(difluoromethoxy)phenyl]hydrazinecarboxamide (known from Chinese patent CN 101715774 A) (CAS 1232543-85-9); 3-(2,2-dichloroethenyl)-2,2-dimethyl-4-(1H-benzimidazol-2-yl)phenylcyclopropanecarboxylic acid ester (known from Chinese patent CN 103524422 A) (CAS 1542271-46-4); methyl ester (4aS)-7-chloro-2,5-dihydro-2-[[(methoxycarbonyl)[4-[(trifluoromethyl)thio]phenyl]amino]carbonyl]indeno[1,2-e][1, 3,4]oxadiazine-4a(3H)-carboxylic acid (known from Chinese patent 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 US 2014/0275503 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-anti)-8- (2-cyclopropylmethoxy-4-trifluoromethylphenoxy)-3-(6-trifluoromethylpyridazin-3-yl)-3-azabicyclo[3.2.1]octane (CAS 933798-27-7), (8-syn)-8-(2 -cyclopropylmethoxy-4-trifluoromethylphenoxy)-3-(6-trifluoromethylpyridazin-3-yl)-3-aza-bicyclo[3.2.1]octane (known from international applications WO 2007040280 A1, WO 2007040282 A1) (CAS 934001-66- 8), N-[3-chloro-1-(3-pyridinyl)-1H-pyrazol-4-yl]-N-ethyl-3-[(3,3,3-trifluoropropyl)thio]propanamide (known from international WO 2015/058021 A1, WO 2015/058028 A1) (CAS 1477919-27-9) and N-[4-(aminothioxomethyl)-2-methyl-6-[(methylamino)carbonyl]phenyl]-3-bromo- 1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamide (known from Chinese patent CN 103265527 A) (CAS 1452877-50-7), 5-(1,3-dioxan-2-yl) -4-[[4-(trifluoromethyl)phenyl]methoxy]pyrimidine (known from international application 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 international applications WO 2010/066780 A1, WO 2011/151146 A1) (CAS 1229023-34 -0), 3-(4-chloro-2,6-dimethylphenyl)-8-methoxy-1-methyl-1,8-diazaspiro[4.5]decane-2,4-dione (known from international application WO 2014/187846 A1) (CAS 1638765-58-8), 3-(4-chloro-2,6-dimethylphenyl)-8-methoxy-1-methyl-2-oxo-1,8-diazaspiro[4.5]dec- ethyl ester 3-en-4-ylcarboxylic acid (known from international applications WO 2010/066780 A1, WO 2011151146 A1) (CAS 1229023-00-0), N-[1-[(6-chloro-3-pyridinyl)methyl]- 2(1H)-pyridinylidene]-2,2,2-trifluoroacetamide (known from German patent DE 3639877 A1, international application WO 2012029672 A1) (CAS 1363400-41-2), [N(E)]-N-[1 -[(6-chloro-3-pyridinyl)methyl]-2(1H)-pyridinylidene]-2,2,2-trifluoroacetamide (known from WO 2016005276 A1) (CAS 1689566-03-7), [N( E)]-N-[1-[(6-chloro-3-pyridinyl)methyl]-2(1H)-pyridinylidene]-2,2,2-trifluoroacetamide (CAS 1702305-40-5), 3-endo- 3-[2-propoxy-4-(trifluoromethyl)phenoxy]-9-[[5-(trifluoromethyl)-2-pyridinyl]oxy]-9-azabicyclo[3.3.1]nonane (known from international applications WO 2011/105506 A1.WO 2016/133011 A1) (CAS 1332838-17-1).

Examples of safeners that can be mixed with the compound(s) and composition according to the present invention are, for example, benoxacor, cloquintocet(-mexyl), cyometrinil, cyprosulfamide, dichlormide, fenchlorazole(-ethyl), fenchlorim, flurazol, fluxofenim, furilazole, isoxadifen (-ethyl), mefenpyr (-diethyl), naphthoic anhydride, oxabethrinyl, 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) .

Examples of herbicides that can be mixed with the compound(s) and composition according to the invention are: acetochlor, acifluorfen, acifluorfen sodium, aclonifen, alachlor, allidochlor, alloxydim, alloxydim sodium, ametrin, amicarbazone, amidochlor, amidosulfuron, 4-amino- 3-chloro-6-(4-chloro-2-fluoro-3-)-5-fluoropyridine-2-carboxylic acid, aminocyclopyrachlor, aminocyclopyrachlor-potassium, aminocyclopyrachloro-methyl, aminopyralid, amitrol, ammonium sulfamate, anilophos, asulam, atrazine , azaphenidin, azimsulfuron, beflubutamide, benazoline, benazolin-ethyl, benfluralin, benfuresate, bensulfuron, bensulfuron-methyl, bensulide, bentazone, benzobicyclone, benzofenap, bicyclopyrone, bifenox, bilanafos, bilanafos-sodium, bispyribac, bispyribac-sodium , bromacil, bromobutide , bromophenoxime, bromoxynil, bromoxynyl-butyrate, -potassium, -heptanoate and -octanoate, busoxinone, butachlor, butafenacil, butamiphos, butenachlor, butralin, butroxydim, butylate, cafenstrol, carbetamide, carfentrazone, carfentrazone-ethyl, chloramben, chlorbromuron, chlorfenac , chlorfenac-sodium, chlorfenprop, chlorflurenol, chlorflurenol-methyl, chloridazone, chlorimuron, chlorimuron-ethyl, chlorophthalim, chlortoluron, chlorthal-dimethyl, chlorsulfuron, cynidone, cynidone-styl, cinmethylin, cinosulfuron, claciphos, cletodym, clodinafop, clodinafop -propargyl, clomazone, clomeprop, clopyralid, cloransulam, cloransulam-methyl, cumiluron, cyanamide, cyanazine, cycloate, cyclopyrimorate, cyclosulfamuron, cyclooxydim, cyhalofop, cyhalofop-butyl, cyprazine, 2,4-D, 2,4-D-butotyl, -butyl , -dimethylamdiolammonium, -diolamine, -ethyl, -2-ethylhexyl, -isobutyl, -isooctyl, -isopropylammonium, -potassium, triisopropanolammonium and -trolamine, 2,4-DB, 2,4-DB-butyl, dimethylammonium, -isooctyl , -potassium and -sodium, daimuron (dimron), dalapon, dazomet, n-decanol, desmedifam, 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, dichloroprop-R, diclofop, diclofop-methyl, diclofop-R -methyl, diclosulam, difenzocquat, diflufenican, diflufenzopyr, diflufenzopyr sodium, dimefuron, dimepiperate, dimetachlor, dimethamethrin, dimethenamide, dimethenamid-R, dimetrasulfuron, dinitramine, dinoterb, diphenamide, diquat, diquat-dibromide, dithiopyr, diuron, DN OC, endothal , EPTC, esprocarb, ethalfluralin, etametsulfuron, etametsulfuron-methyl, etiosin, etofumesate, ethoxyphene, ethoxyphen-ethyl, ethoxysulfuron, etobenzanide, 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, viz. 3-[7-chloro-5-fluoro- 2-(trifluoromethyl)-1H-benzimidazol-4-yl]-1-methyl-6-(trifluoromethyl)pyrimidine-2,4(1H,3H)-dione, fenoxaprop, fenoxaprop-R, fenoxaprop-ethyl, fenoxaprop-R -ethyl, fenoxasulfone, fenquinotrion, fentrazamide, flamprop, flamprop-M-isopropyl, flamprop-M-methyl, flazasulfuron, florasulam, fluazifop, fluazifop-R, fluazifop-butyl, fluazifop-R-butyl, flucarbazone, flucarbazone-sodium, flucetosulf damage , fluchloralin, flufenacet, flufenpyr, flufenpyr-ethyl, flumetsulam, flumiclorac, flumiclorac-pentyl, flumioxazine, fluometuron, flurenol, flurenol-butyl, -dimethylammonium and -methyl, fluorglycofen, fluorglycofene-ethyl, flupropanate, flupyrsulfuron, flupyrsulfuron-methyl -sodium , fluridone, flurochloridone, fluroxypyr, fluroxypyr-methyl, flurtamone, fluthiacet, fluthiacet-methyl, fomezafen, fomezafen sodium, foramsulfuron, fosamine, glufosinate, ammonium glufosinate, glufosinate-P-sodium, glufosinate-P-ammonium, glufosinate-P -sodium, glyphosate, glyphosate-ammonium, -isopropylammonium, -diammonium, dimethylammonium, -potassium, -sodium and -trimesium, H-9201, i.e. O-(2,4-dimethyl-6-nitrophenyl)-O-ethylisopropylphosphoramidothioate, haloxifen, haloxifen-methyl, halosophen, halosulfuron, halosulfuron-methyl, haloxifop, haloxyfop-R, haloxifop-ethoxyethyl, haloxifop-P-ethoxyethyl, haloxifop-methyl, haloxifop-R-methyl, hexazinon, HW-02, i.e. 1- (dimethoxyphosphoryl)ethyl(2,4-dichlorophenoxy)acetate, imazamethabenz, imazametabenz-methyl, imazamox, imazamox-ammonium, imazapik, imazapir-ammonium, imazapir, imazapyr-isopropylammonium, imazaquin, imazaquin-ammonium, imazethapyr, imazethapyr-ammonium, imazosesulfuron , indanophane, indaziflam, iodosulfuron, iodosulfuron-methyl-sodium, ioxynil, ioxynyl-octanoate, -potassium and -sodium, ipfencarbazone, isoproturon, isouron, isoxaben, isoxaflutol, carbutylate, KUH-043, i.e. 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, -dimethylammonium, -2-ethylhexyl, -isopropylammonium, -potassium and -sodium, MSRV, MSRV-methyl, -ethyl and -sodium, mecoprop, mecoprop-sodium and -butotyl, mecoprop-P , mecoprop-P-butotyl, dimethylammonium, -2-ethylhexyl and -potassium, mefenacet, mefluidide, mesosulfuron, mesosulfuron-methyl, mesotrione, metabenzthiazuron, metam, metamifop, metamitron, metazachlor, metazosulfuron, metabenzthiazuron, metiopyrsulfuron, metiozolin, methylisothiocyt anat, metobromuron , metolachlor, S-metolachlor, methosulam, methoxuron, metribuzin, metsulfuron, metsulfuron-methyl, molinate, monolinuron, monosulfuron, monosulfuron ester, MT-5950 i.e. N-(3-chloro-4-isopropylphenyl)-2-methylpentanamide , NGGC-011, napropamide, NC-310 i.e. [5-(benzyloxy)-1-methyl-1H-pyrazol-4-yl](2,4-dichlorophenyl)methanone, neburon, nicosulfuron, nonanoic acid (pelargonic acid ), norflurazone, oleic acid (fatty acids), orbencarb, orthosulfamuron, oryzalin, oxadiargyl, oxadiazon, oxasulfuron, oxaziclomefon, oxyfluorfen, paraquat, paraquat dichloride, pebulate, pendimethalin, penoxsulam, pentachlorophenol, pentoxazone, pentoxamide, petroleum oils, phenmedipam, picloram Picolineaphin, Pinoginaphen, Piperofos, Pretyahlor, Primisulfuron, Primisulfuron-Meadtil, Diamine, Profoxymma, Profoxim, Promiton, Prometrin, Perekhalor, Distributed, Proscovaphop, Propham, Propisochlor, Propoxicarbazon, Propoxicarbazon-Natrios, Pyrisifuro, Pepishamid, Sprisomids, Speesamids, Speesamids, Speesamids, Speesamids, Speesamid , Navefuron, Pyraclonil , pyraflufen, pyraflufen-ethyl, pyrasulfotol, pyrazolinate (pyrazolate), pyrazosulfuron, pyrazosulfuron-ethyl, pyrazoxyfen, pyribambenz, pyribambenz-isopropyl, pyribambenz-propyl, pyribenzoxime, pyributicarb, pyridafol, pyridate, pyrifthalide, pyriminobac, pyriminobac -methyl, pyrimisulfan, pyrithiobac, pyrithiobac sodium, pyroxasulfone, pyroxulam, quinclorac, quinmerac, quinoclamin, quizalofop, quizalofop-ethyl, quizalofop-R, quizalofop-p-ethyl, quizalofop-p-tefuryl, rimsulfuron, saflufenacil, setoxydim, siduron, simazine, simetrin, SL-261, sulcotrione, 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-thioxoimidazolidin-4,5-dione, 2,3,6-TBA, TCA (trichloroacetic acid), TCA-sodium, tebuthiuron, tefuryltrione, tembotrione, tepraloxydim, terbacil, terbucarb, terbumetone, terbutylazine, terbutrin, tenylchlor, thiazopyr, thiencarbazone, thiencarbazone-methyl, thiensulfuron, thiensulfuron-methyl, thiobencarb, thiafenacil, tolpyralate, topramesone, tralkoxydim, triafamone, triallat, triasulfuron, triaziflam, tribenuron, tribenuron-methyl, triclopyr, trietazine, trifloxysulfuron, trifloxysulfuron-sodium, trifludimoxazine, trifluralin, triflusulfuron, triflusulfuron-methyl, tritosulfuron, urea sulfate, vernolate, XDE-848, ZJ-0862, i.e. 3,4-dichloro-N -{2-[(4,6-dimethoxypyrimidin-2-yl)oxy]benzyl}aniline and the following compounds:

Examples of plant growth regulators are:

acibenzolar, acibenzolar-S-methyl, 5-aminolevulinic acid, ancimidol, 6-benzylaminopurine, brassinolide, catechin, chlormequat chloride, cloprop, cyclanilide, 3-(cycloprop-1-enyl)propionic acid, daminoside, dazomet, n-decanol, dikegulac, dikegulac-sodium, endothal, endothal-dicalium, -disodium and -mono(N,N-dimethylalkylammonium), ethephon, flumetraline, flurenol, flurenol-butyl, flurprimidol, forchlorfenuron, gibberellic acid, inabenfide, indole-3-acetic acid (IAA), 4-indol-3-ylbutyric acid, isoprothiolane, probenazole, jasmonic acid, maleic acid hydrazide, mepiquat chloride, 1-methylcyclopropene, methyl jasmonate, 2-(1-naphthyl)acetamide, 1-naphthylacetic acid, 2-naphthyloxyacetic acid, nitrophenolate mixture, paclobutrazol, N-(2-phenylethyl)-beta-alanine, N-phenylphthalamic acid, prohexadione, prohexadione-calcium, prohydrojasmone, salicylic acid, strigolactone, teknazen, thidiazuron, triacontanol, trinexapac, trinexapak-ethyl, cytodef , uniconazole, uniconazole-R.

Methods and Applications

The compound(s) and composition according to the invention have a strong potential for modulating plant protection. They can be used to fight unwanted bacteria, in particular bacteria of the genus Xanthomonas. The compound(s) and composition according to the invention can be used to protect seeds, germinating seeds, germinating seedlings, plants, plant parts, fruits, crops and/or the soil in which the plants grow.

The term "control" in the context of this document includes the preventive, protective, curative and destructive effect on unwanted microorganisms.

Thus, the present invention relates to a method for combating bacterial diseases caused by bacteria of the genus Xanthomonas, comprising the step of applying at least one compound according to the invention or at least one composition according to the invention to plants, plant parts, seeds, fruits or soil, in which plants grow.

Generally, when the compound(s) and composition of the invention are used in therapeutic or protective methods for combating bacterial diseases, an effective and plant-compatible amount is applied to the plants, plant parts, fruits, seeds, or to the soil or substrates on which the plants grow. . Suitable substrates that can be used for growing plants include inorganic based substrates such as mineral wool, in particular stone wool, perlite, sand or gravel; organic substrates such as peat, pine bark or sawdust; and hydrocarbon-based substrates such as polymeric foams or plastic beads. An effective and plant compatible amount means an amount which is sufficient to control bacteria present or likely to occur on arable land and which does not entail any noticeable symptoms of phytotoxicity for said crops. Such an amount may vary widely depending on the pathogens to be controlled, the type of crop, the growth stage of the culture, the climatic conditions and the respective compound(s) or composition of the invention used. This amount can be determined by systematic field trials, which are within the ability of a person skilled in the art. Diseases caused by bacterial pathogens, e.g. Xanthomonas spp. (e.g. Xanthomonas campestris pv, Oryzae), Pseudomonas spp. (e.g. Pseudomonas syringae pv. Lachrymans), Erwinia spp. (e.g. Erwinia amylovora) can be controlled with the compounds of the present invention . The compounds of formula (II) may also be effective in controlling phytopathogenic fungi on plants.

Plants and parts of plants

The compound(s) and composition according to the invention can be applied to any plant or plant part.

Plants means all plants and plant populations, such as desired and undesired wild plants or crop plants (including naturally occurring crop plants). Cultivated plants can be plants that can be obtained using conventional breeding and optimization methods, or using biotechnological and genetic engineering methods, or combinations of these methods, including genetically modified plants (GMO or transgenic plants) and plant varieties that are protected or unprotected by selection rights.

Genetically Modified Plants (GMOs)

Genetically modified plants (GMO or transgenic plants) are plants in which a heterologous gene has been stably integrated into the genome. The term "heterologous gene" generally means a gene that is produced or assembled outside of a plant and introduced into the cell nucleus genome, chloroplast genome, or mitochondrial genome. This gene imparts new or improved agronomic or other characteristics to the transformed plant by expressing the protein or polypeptide of interest, or by inhibiting or turning off other gene(s) that are present in that plant (by using e.g. antisense DNA technology, cosuppression technology, RNA interference - RNAi-technologies or microRNA - miRNA-technologies). A heterologous gene that is present in the genome is also called a transgene. A transgene that is defined through its specific location in the plant genome is called a transformational or transgenic event.

Cultivars are understood to mean plants that have new properties (“traits”) and have been obtained by conventional crossing, mutagenesis or recombinant DNA methods. These can be varieties, varieties, bio- or genotypes.

Plant parts should be understood as all parts and organs of plants located above the ground and under the ground, such as shoots, leaves, needles, trunks, stems, flowers, fruiting bodies, fruits, seeds, roots, tubers and rhizomes. Plant parts also include the harvested crop as well as vegetative and generative propagation material such as cuttings, tubers, rhizomes, shoots and seeds.

Plants that can be treated according to the methods of the invention include the following: cotton, flax, vine, fruits, vegetables such as Rosaceae sp. such as apricots, cherries, almonds and peaches, and berry crops such as strawberries), Ribesioidae sp., Jugiandaceae sp., Betuiaceae sp., Anacardiaceae sp., Fagaceae sp., Moraceae sp., Oleaceae sp., Actinidaceae sp., Lauraceae sp., Musaceae sp. (e.g. banana trees and plantations), Rubiaceae sp. (e.g. coffee), Theaceae sp., Sterculiceae sp., Rutaceae sp. (eg lemons, oranges and grapefruits); Solanaceae sp. (e.g. tomatoes), LHiaceae sp., Asteraceae sp. (e.g. lettuce), Umbelliferae sp., Cruciferae sp., Chenopodiaceae sp., Cucurbitaceae sp. (e.g. cucumbers), Alliaceae sp. (e.g. leek, onion), PapHionaceae sp. (for example, peas); major industrial crops such as Gramineae sp. (eg corn, lawn grass, cereals such as wheat, rye, rice, barley, oats, millet and triticale), Asteraceae sp. (e.g. sunflower), Brassicaceae sp. (e.g. white cabbage, red cabbage, broccoli, cauliflower, Brussels sprouts, Chinese cabbage, kohlrabi, radish, as well as oilseed rape, mustard, horseradish and watercress), Fabacae sp. (e.g. beans, peanuts), PapHionaceae sp. (e.g. soybeans), Solanaceae sp. (e.g. potatoes), Chenopodiaceae sp. (e.g. sugar beet, fodder beet, chard, table beet); industrial crops and ornamental plants for gardens and woodlands; and genetically modified varieties of each of these plants.

Plants and plant varieties that can be treated using the methods disclosed above include plants and plant varieties that are resistant to one or more biotic stresses, that is, the above plants show improved protection against animal or microbial pests, such as , against nematodes, insects, mites, phytopathogenic fungi, bacteria, viruses and/or viroids.

Plants and plant varieties that can be treated using the methods disclosed above include those plants that are resistant to one or more abiotic stresses. Abiotic stress conditions may include, for example, drought, exposure to cold temperatures, exposure to heat, osmotic stress, perched water, increased soil salinity, exposure to increased salinity, ozone exposure, high irradiation conditions, limited availability of nitrogen fertilizers, limited availability of phosphate fertilizers, lack of shading.

Plants and plant varieties that can be treated using the methods disclosed above include those plants that are characterized by increased yields. Increased yields in these plants may result, for example, from improved plant physiology, growth and development, as well as water use efficiency, water retention efficiency, improved nitrogen uptake efficiency, increased carbon assimilation, improved photosynthesis, enhanced germination efficiency, and accelerated maturation. In addition, yield can be affected by improved plant architecture (under stressed and non-stressed conditions), including, but not limited to, early flowering, flowering control for hybrid seed production, germination ability, plant size, number of nodes and spacing, root development, embryo size, fruit size, pod size, number of pods or ears, number of buds per pod or ear, bud weight, increased bud filling, reduced bud loss, reduced pod cracking, and resistance to lodging. Other yield characteristics include germ composition such as carbohydrate content and composition such as cotton or starch, protein content, oil content and composition, nutritional value, reduced nutritional detrimental compounds, improved processability, and improved shelf life.

Plants and plant varieties that can be treated using the methods disclosed above include plants and plant varieties that are hybrid plants that already express heterosis properties or hybrid effect, which generally leads to increased yield, increased rapid growth ability, health and resilience to biotic and abiotic stresses.

Plants and plant varieties (obtained by plant biotechnology methods such as genetic engineering) that can be treated using the methods disclosed above include plants and plant varieties that are herbicide resistant plants, that is, plants that have become resistant to towards one or more given herbicides. Such plants can be obtained either by genetic transformation or by breeding plants containing a mutation conferring such herbicide resistance.

Plants and plant varieties (obtained by plant biotechnology methods such as genetic engineering) that can be treated using the methods disclosed above include plants and plant varieties that are insect-resistant transgenic plants, that is, plants that have acquired resistance to attack by certain predetermined insects. Such plants can be obtained by genetic transformation or by breeding plants containing a mutation conferring such insect resistance.

Plants and plant varieties (obtained by plant biotechnology methods, such as genetic engineering) that can be treated using the methods disclosed above include plants and plant varieties that are disease-resistant transgenic plants, that is, plants that have acquired resistance to attack by certain predetermined insects. Such plants can be obtained by genetic transformation or by breeding plants containing a mutation conferring such insect resistance.

Plants and plant varieties (obtained by plant biotechnology methods such as genetic engineering) that can be treated using the methods disclosed above include plants and plant varieties that are resistant to abiotic stresses. Such plants can be obtained by genetic transformation or by breeding plants containing a mutation conferring such stress resistance.

Plants and plant varieties (obtained by plant biotechnology methods such as genetic engineering) that can be processed using the methods disclosed above include plants and plant varieties that exhibit an altered quantity, quality and/or storage stability of the harvested crop and/or altered properties of certain components of the harvested crop.

Plants and plant varieties (obtained by plant biotechnology methods such as genetic engineering) that can be treated using the methods disclosed above include plants and plant varieties, such as cotton, with altered fiber properties. Such plants can be obtained by genetic transformation or by breeding plants that contain a mutation conferring such altered fiber properties.

Plants and plant varieties (obtained by plant biotechnology methods such as genetic engineering) that can be treated using the methods disclosed above include plants and plant varieties, such as oilseed rape or related plants of the Brassica family, with altered oil composition properties. Such plants can be obtained by genetic transformation or by breeding plants that contain a mutation conferring such altered properties on the composition of the oils.

Plants and plant varieties (obtained by plant biotechnology, such as genetic engineering) that can be treated using the methods disclosed above include plants and plant varieties, such as oilseed rape or related plants of the Brassica family, with altered seed shattering properties. Such plants can be obtained by genetic transformation or by breeding plants that contain a mutation conferring such altered seed shattering properties and include plants, such as oilseed rape plants, with delayed or reduced seed shattering.

Plants and plant varieties (obtained by plant biotechnology methods such as genetic engineering) that can be processed using the methods disclosed above include plants and plant varieties, such as tobacco plants, with altered post-translational protein modification patterns.

Aspects of the present description may be further understood in light of the following examples, which should not be construed as limiting the scope of the present description in any way.

EXAMPLES

Synthesis of compounds of formula (II)

Production Example 1: Preparation of methyl N-[(3,4,5-trichloro-2-thienyl)carbonyl]glycinate (compound 11.01)

0.0, 23 ml (1.62 mmol) of triethylamine followed by 1.0 ml (1.68 mmol) of a 50% (w/w) solution of propanephosphonic anhydride in ethyl acetate. The reaction mixture was stirred at room temperature for 20 hours. This reaction mixture was quenched with water and extracted with ethyl acetate. The combined organic layers were dried over magnesium sulfate, filtered and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (n-heptane/ethyl acetate gradient) to give 178 mg (93% purity, 51% yield) of methyl N-[(3,4,5-trichloro-2-thienyl)carbonyl]glycinate as white solid. LogP=2.8. (M+H)=302.

Preparation Example 2: Preparation of N-[(3,4,5-trichloro-2-thienyl)carbonyl]glycine (compound 11.05)

To a solution of 178 mg (0.59 mmol) of methyl-N-[(3,4,5-trichloro-2-thienyl)carbonyl]glycinate dissolved in 3 ml of tetrahydrofuran, 1.3 ml of a 1M aqueous solution of lithium hydroxide was added dropwise (1.3 mmol). The reaction mixture was stirred at room temperature for 4 hours. This reaction mixture was diluted with ethyl acetate, water and saturated aqueous sodium bicarbonate. The organic layer was washed twice with saturated sodium bicarbonate aqueous solution. The combined aqueous layers were carefully acidified with 37% (w/w) aqueous hydrochloric acid at 0° C. and extracted with ethyl acetate. The combined organic layers were dried over magnesium sulfate, filtered and concentrated under reduced pressure to give 159 mg (98% purity, 92% yield) of N-[(3,4,5-trichloro-2-thienyl)carbonyl]glycine as a white solid substances. logp=2.14. (M-N)=286.

Production Example 3: Preparation of Ethyl 1-{[(3,4,5-trichloro-2-thienyl)carbonyl]amino}cyclopropanecarboxylate (Compound II.02)

Step 1: Preparation of ethyl 1-{[(3-amino-4,5-dichloro-2-thienyl)carbonyl]amino}cyclopropanecarboxylate (Compound XVIIc.01)

To a solution of 150 mg (0.60 mmol) of 3-amino-4,5-dichlorothiophene-2-carboxylic acid hydrochloride (1:1) (compounds XIXc.01) and 255 mg (1.50 mmol) of ethyl-1-hydrochloride aminocyclopropanecarboxylate (1:1), dissolved in 4.0 ml of dichloromethane, was added 0.45 ml (2.59 mmol) of N,N-diisopropylethylamine, and then a solution of 255 mg (1.50 mmol) of 2-chloro-1 chloride, 3-dimethylimidazolinium in 2.0 ml dichloromethane. The reaction mixture was stirred at room temperature for 16 hours. This reaction mixture was quenched with water and extracted with dichloromethane. The combined organic layers were dried over magnesium sulfate, filtered and concentrated under reduced pressure. The residue was purified by preparative HPLC (acetonitrile/aqueous formic acid (1%) gradient) to give 69 mg (100% purity, 35% yield) of ethyl 1-{[(3-amino-4,5-dichloro-2 -thienyl)carbonyl]amino}cyclopropanecarboxylate as a white solid. LogP=2.77. (M+H)=323.

Step 2: Preparation of ethyl 1-{[(3,4,5-trichloro-2-thienyl)carbonyl]amino}cyclopropanecarboxylate (compound II.02). To a solution of copper chloride (I) (9.8 mg, 0.10 mmol) in 0.5 ml of anhydrous acetonitrile was added dropwise tert-butyl nitrite (13 μl, 0.10 mmol) at 0°C. The reaction mixture was allowed to warm to room temperature before adding dropwise a solution of 25 mg (0.06 mmol) of ethyl 1-{[(3-amino-4,5-dichloro-2-thienyl)carbonyl]amino}cyclopropanecarboxylate in 0.5 ml of anhydrous acetonitrile. The reaction mixture was stirred at room temperature for 3 hours. This reaction mixture was diluted with dichloromethane and carefully acidified with 1M aqueous hydrochloric acid. The aqueous layer was extracted twice with dichloromethane. The combined organic layers were dried over magnesium sulfate, filtered and concentrated under reduced pressure. The residue was purified by preparative HPLC (acetonitrile/aqueous formic acid (1%) gradient) to give 12 mg (93% purity, 48% yield) of ethyl 1-{[(3,4,5-trichloro-2-thienyl )carbonyl]amino}cyclopropanecarboxylate as a beige solid. LogP=3.40. (M)=341.

Connection examples

Compounds according to the invention, shown in tables II.1, II.2, II.3, II.4 and II.5, were obtained by analogy with the examples above, and/or in accordance with the general description of the methods disclosed here. These compound examples are racemates unless otherwise noted.

The following table II.1 illustrates, in a non-limiting manner, examples of compounds according to formula (II).

Examples of intermediate compounds according to the invention, which are shown in the following tables, were obtained in analogy with the examples presented above, and/or in accordance with the general description of the methods disclosed in this document.

The following table II.2 non-limitingly illustrates examples of intermediates according to formulas (XVIa) and (XVIb).

The following table II.3 non-limitingly illustrates examples of intermediates according to formula (XVIc).

The following table II.4 non-limitingly illustrates an example of intermediates according to

The following table II.5 non-limitingly illustrates an example of intermediates according to formula (XIXc).

In the tables above, the measurement of LogP values was carried out in accordance with EEC directive 79/831, annex V.A8, using HPLC (high performance liquid chromatography) on reverse phase columns using the following methods:

^[a] The LogP value is determined by measuring LC-UV in the acid range, with 0.1% formic acid in water and acetonitrile as eluent (linear gradient from 10% acetonitrile to 95% acetonitrile).

^[b] The LogP value is determined by neutral range LC-UV measurement, with 0.001 molar ammonium acetate in water and acetonitrile as eluent (linear gradient from 10% acetonitrile to 95% acetonitrile).

^[c] The LogP value is determined by measuring LC-UV in the acid range, with 0.1% phosphoric acid and acetonitrile as eluent (linear gradient from 10% acetonitrile to 95% acetonitrile).

If more than one LogP value is available within the same method, then all values are listed and separated by a "+" sign.

Calibration was performed with straight chain alkan-2-ones (having 3 to 16 carbon atoms) with known LogP values (measurement of LogP values using retention times with linear interpolation between successive alkanones). Lambda maximum values were determined using UV spectra from 200 to 400 nm and peak values of chromatographic signals.

NMR Peak Lists

Table A presents NMR data ( ¹ H) of some of the compounds disclosed in the above tables.

¹ H-NMR data of selected examples are recorded as ¹ H-NMR peak lists. For each signal peak, the value of δ is given in ppm. and signal intensity in parentheses. Between the pairs "value δ - signal intensity" semicolons are placed as separators.

Thus, the list of peaks for the example is of the form:

δ ₁ (intensity ₁ ); δ ₂ (intensity ₂ );…; δ _i (intensity _i );…; δ _n (intensity _n ).

The intensity of narrow signals correlates with the height of these signals in the decoded example of the NMR spectrum in cm and shows the real ratios of the signal intensities. From wide signals, several peaks or the middle of the signal and their relative intensity compared to the most intense signal in the spectrum can be shown.

To calibrate the chemical shift for ¹ H spectra, we use tetramethylsilane and/or the chemical shift of the solvent used, especially in the case of spectra measured in DMSO (DMSO). Therefore, in the lists of NMR peaks, the peak of tetramethylsilane may occur, but not necessarily.

The ¹ H-NMR peak lists are similar to the classic ¹ H-NMR transcripts and therefore usually contain all the peaks that are listed in the classic NMR interpretation.

In addition, they can show signals similar to the classical ¹ H-NMR transcripts of solvents, stereoisomers of target compounds that are also the subject of the invention, and/or impurity peaks.

To show compounds in the delta range for solvents and/or water, common solvent peaks, eg DMSO peaks in DMSO-D ₆ and water peak, are shown in our ¹ H-NMR peak lists and typically have a high average intensity.

Peaks of stereoisomers of the target compounds and/or peaks of impurities usually have an average lower intensity than the peaks of the target compounds (for example, >90% purity).

Such stereoisomers and/or impurities may be typical of a particular production process. Therefore, their peaks can help to recognize the reproduction of our method of preparation through "characteristics of by-products".

An expert who calculates target compound peaks using known methods (MestreC, ACD modeling, as well as empirically estimated expected values) can highlight target compound peaks as needed, optionally using additional intensity filters. This selection will be similar to the selection of the corresponding peak in the classical interpretation of ¹ H-NMR.

For more details on describing NMR peak list data, see "Citation of NMR Peaklist Data within Patent Applications" in Research Disclosure Database Number 564025.

BIOLOGICAL DATA

Example A: Xanthomonas campestris pv. campestris in vitro cell test

Solvent: DMSO

Culture medium: LB broth medium (Luria Broth Miller) Sigma

Inoculum: bacterial suspension

Compounds to be tested were solubilized in DMSO and this solution was used to prepare the required concentration range. The final concentration of DMSO used in the assay was <**1%.

The inoculum was prepared from a pre-culture of bacteria grown in liquid medium and diluted to the desired optical density (OD).

Compounds were evaluated for their ability to inhibit bacterial growth in a liquid medium culture assay. The compounds were added at the desired concentrations to the culture medium containing the bacterial suspension. After 24 hours of incubation, the potency of the compounds was determined by spectrometric measurement of bacterial growth. Suppression was determined by comparing absorbance values in wells containing compounds with absorbance values in control wells without compounds.

In this test, the following compounds according to the invention showed no direct activity at a test compound concentration of 20 ppm: II.01; II.02; II.03; II.04; II.06; II.07; II.08; II.09; II.10; II.11; II.12; II.13; II.14; II.15; II.16; II.17; II.18; II.19; II.20; II.21; II.22; II.23; II.24; II.35; II.36.

Example B: in vivo prophylactic test for Xanthomonas campestris pv. campestris (black rot on cabbage)

Test compounds were prepared by homogenization in acetone/dimethylsulfoxide/tween® and then diluted with water to obtain the desired concentration.

Young cabbage plants were treated by spraying with the compound prepared as described above. Control plants were treated with an aqueous solution of acetone/dimethylsulfoxide/tween® only.

After 72 hours, these plants were infected by spraying the leaves with an aqueous suspension of Xanthomonas campestris pv. campestris. Infected cabbage plants were incubated for 8 or 10 days at 27° C. and 95% relative humidity.

Evaluation was carried out 8 or 10 days after inoculation. 0% means efficiency, which corresponds to the efficiency of control plants, while 100% efficiency means that no disease was observed.

In this test, the following compounds according to the invention showed an efficiency between 70% and 79% at a test compound concentration of 31 ppm: II.02; II.31; II.35.

In this test, the following compounds according to the invention showed efficacy between 80% and 89% at a test compound concentration of 31 ppm: II.03; II.04; II.15.

In this test, the following compounds according to the invention showed efficacy between 90% and 100% at a test compound concentration of 31 ppm: II.01; II.06; II.14; II.36.

Example C: comparative examples

Compounds CMP1 and CMP2 were tested in an in vivo prophylactic test against Xanthomonas campestris pv, campestris (black rot on cabbage) under the same conditions as described in Example B.

Compounds CMP1 and CMP62 were prepared as described in US Pat. No. 5,534,541.

The results are shown in the table below.

Example D: Induction of Defense Gene Expression in Arabidopsis thaliana

Reporter plants of Arabidopsis thaliana containing a green fluorescent protein (GFP) coding sequence linked to a salicylate-responsive PR1 gene promoter sequence (Pathogenesis Related Protein I) (AT2G14610) were grown for five days and then sprayed with the compounds. On day 3 after spraying, plant fluorescence was assessed using a MacroFluo instrument from Leica Microsystems (Wetzlar, Germany). Fluorescence was quantified using Meta-Morph Microscopy Automation & Image Analysis Software (Molecular Devices, Sunnyvale, CA, USA).

Background fluorescence in sham-treated leaves was set to 1.00. Treatment with salicylic acid (300 ppm) resulted in a relative fluorescence value of 2.70, confirming the validity of the test system.

In this test, the following compounds according to the invention showed a relative fluorescence value of at least more than 2 at a compound concentration of 300 ppm: II.01; II.02; II.03; II.04; II.05; II.07; II.08; II.09; II.10; II.11; II.12; II.13; II.14; II.15; II.17; II.18; II.19; II.20; II.22; II.23; II.24; II.25; II.26; II.30; II.31; II.32; II.33; II.35; II.36; II.37.

In this test, the following compounds according to the invention showed a relative fluorescence value of at least more than 2 at a compound concentration of 75 ppm: II.16; II.28.

Salicylate acts as the main protective hormone against plant pathogens. All of the compounds described above stimulate the salicylic acid metabolic pathway and therefore can protect plants from a wide range of pathogens.

Claims (13)

1. Compound of formula (II):

wherein R ¹ , R ² and R ³ represent a chlorine atom; R ⁴ is selected from the group consisting of hydrogen, 2-methylpropyl, 1-methylpropyl, cyclopropyl, cyclopropyl substituted with 2-6 carbon alkenyl, benzyl and benzyl substituted with hydroxyl, and R ⁵ represents a hydrogen atom; or R ⁴ and R ⁵ together with the carbon atom to which they are attached form cyclopropyl; R ⁶ is selected from the group consisting of hydrogen atom, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 cyanoalkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl , cycloalkyl with 3-8 carbon atoms, phenyl, benzyl, -C ₁ -C ₆ -alkyl-Si(C ₁ -C ₆ -alkyl) ₃ and -C _{1 -C 6} -alkyl-C ₃ -C ₈ -cycloalkyl ; R ⁷ represents a hydrogen atom or alkyl with 1-6 carbon atoms. 2. The compound of formula (II) according to claim 1, where R ⁶ is selected from the group consisting of a hydrogen atom, alkyl with 1-6 carbon atoms, haloalkyl with 1-6 carbon atoms, cyanoalkyl with 1-6 carbon atoms, alkenyl with 2-6 carbon atoms, alkynyl with 2-6 carbon atoms, cyclopropyl, phenyl, benzyl, -C ₁ -C ₆ -alkyl-Si(C ₁ -C ₆ -alkyl) ₃ and -C ₁ -C ₆ -alkylcyclopropyl. 3. The compound of formula (II) according to claim 1, where R ⁷ represents a hydrogen atom or methyl. 4. A compound of formula (II) according to any one of claims 1 to 3, wherein R ⁴ is hydrogen or isobutyl. 5. A compound of formula (II) according to any one of claims 1 to 3, wherein R ⁴ and R ⁵ together with the carbon atom to which they are attached form cyclopropyl.