Pyrazolylcarboxanilides

ES 2 313 615 T3

DESCRIPTION

Pyrazolylcarboxanilides.

The present invention relates to new pyrazolylcarboxanilides, to various processes for their preparation and to their use to combat harmful microorganisms in plant protection and material protection.

It is already known that multiple carboxanilides possess fungicidal properties (see, for example, WO 03/070705, EP 0545099 and JP 9132567). The activity of the substances described there is good but leaves something to be desired in many cases with low amounts of application.

New pyrazolylcarboxanilides of formula (I) have been found

<img file="ES2313615T3_D0001.tif" />

in which

R represents difluoromethyl or trifluoromethyl and

R¹ represents chlorine or methyl.

Furthermore, it has been found that pyrazolylcarboxanilides of formula (I) are obtained by reacting

a) pyrazolylcarboxylic acid halides of formula (II)

<img file="ES2313615T3_D0002.tif" />

in which

R has the meanings given above and

X¹ represents halogen, with aniline derivatives of formula (III)

<img file="ES2313615T3_D0003.tif" />

in which R¹ has the meanings given above, optionally in the presence of an acid binder and optionally in the presence of a diluent, or by reacting

ES 2 313 615 T3

b) halogenopyrazolylcarboxanilides of formula (IV)

<img file="ES2313615T3_D0004.tif" />

in which

R has the meanings given above and

X² represents bromine or iodine, with boronic acid derivatives of formula (V)

<img file="ES2313615T3_D0005.tif" />

in which

R¹ has the meanings given above and

G¹ and G² they represent respectively hydrogen or together tetramethylethylene, in the presence of a catalyst, optionally in the presence of an acid binder and optionally in the presence of a diluent, or by reacting

c) halogenopyrazolylcarboxanilides of formula (IV)

<img file="ES2313615T3_D0006.tif" />

in which

R has the meanings given above and

X² represents bromine or iodine, in a first step with a diborane derivative of formula (VI)

G - 0 OG⁴

BB (VI)

G— OO ~ G³

ES 2 313 615 T3 in which

G³ and G⁴ represent respectively alkyl or jointly alkanediyl, in the presence of a catalyst, optionally in the presence of an acid binder and optionally in the presence of a diluent and without processing in a second stage with halogenobenzene derivatives of formula (VII)

<img file="ES2313615T3_D0007.tif" />

in which

R¹ has the meanings given above and

X³ represents bromine, iodine or trifluoromethylsulfonyloxy, in the presence of a catalyst, optionally in the presence of an acid binder and optionally in the presence of a diluent.

Finally, it has been found that the new pyrazolylcarboxanilides of formula (I) possess very good microbicidal properties and can be used to combat unwanted microorganisms both in plant protection and in the protection of materials.

Surprisingly, the pyrazolylcarboxanilides of formula (I) according to the invention show an essentially better fungicidal activity than the constitutionally more similar active principles previously known with the same effect.

Pyrazolylcarboxanilides according to the invention are generally defined by formula (I). Formula (I) summarizes the following four pyrazolylcarboxanilides:

N- (4'-chloro-3 ', 5-difluorobiphenyl-2-yl) -3- (difluoromethyl) -1-methyl-1H-pyrazole-4-carboxamide

N- (4'-chloro-3 ', 5-difluorobiphenyl-2-yl) -1-methyl-3- (trifluoromethyl) -1H-pyrazole-4-carboxamide

N- (3 ', 5-difluoro-4'-methylbiphenyl-2-yl) -1-methyl-3- (difluoromethyl) -1H-pyrazole-4-carboxamide

N- (3 ', 5-difluoro-4'-methylbiphenyl-2-yl) -1-methyl-3- (trifluoromethyl) -1H-pyrazole-4-carboxamide

If, for example, 1-methyl-3- (trifluoromethyl) -1H-pyrazole-4-carbonyl chloride and 4'-chloro-3 ', 5-difluoro-1,1'biphenyl-2-amine are used as substances starting point as well as a base, then the course of process a) according to the invention can be explained by the following reaction equation:

<img file="ES2313615T3_D0008.tif" />

The pyrazolylcarboxylic acid halides required as starting substances for carrying out the process a) according to the invention are generally defined by the formula (II). In this formula (II) R represents difluoromethyl or trifluoromethyl. X¹ preferably represents chlorine.

ES 2 313 615 T3

The pyrazolylcarboxylic acid halides of formula (II) are known and / or can be prepared according to known procedures (see, for example, JP 01290662 and US 5,093,327).

The aniline derivatives required as starting substances for carrying out the process a) according to the invention are generally defined by the formula (III). In this formula (III) R¹ represents chlorine or methyl.

The aniline derivatives of formula (III) are known or can be prepared according to known procedures (see WO 03/070705).

If N- (2-bromo-2-fluorophenyl) -1-methyl-3- (trifluoromethyl) -1H-pyrazole-2-carboxamide and 2-chloro-3-fluorophenylboronic acid are used as starting substances as well as a catalyst and a base, then the course of process b) according to the invention can be explained with the following reaction equation:

<img file="ES2313615T3_D0009.tif" />

The halogenopyrazolylcarboxanilides required as starting substances for carrying out the process b) according to the invention are generally defined by the formula (IV). In this formula (IV) R represents difluoromethyl or trifluoromethyl. X² preferably represents bromine or iodine.

Halogenopyrazolylcarboxanilides of formula (IV) are known (see WO 03/070705).

The boronic acid derivatives required as starting substances for carrying out process b) according to the invention are generally defined by the formula (V). In this formula (V) R¹ represents chlorine or methyl. G¹ and G² they preferably represent respectively hydrogen or together tetramethylethylene.

Boronic acids of formula (V) are known synthetic chemicals. These can also be prepared immediately before the reaction directly from halogenobenzene derivatives and boronic acid esters and reacted without further processing.

If, for example, N- (2-bromo-2-fluorophenyl) -1-methyl-3- (trifluoromethyl) -1H-pyrazole-2-carboxamide and 2,2,2 ', 5,5,5' are used , 5'-octamethyl-2,2'-bi-1,3,2-dioxaborolane in the first stage and additionally 5-bromo-2-chloro-1-fluorobecene in the second stage as starting substances, as well as in any stage a catalyst and a base, then the course of process c) according to the invention can be explained by the following reaction equation:

<img file="ES2313615T3_D0010.tif" />

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The halogenopyrazolylcarboxanilides of formula (IV) required as starting substances for carrying out process c) according to the invention have already been described above in connection with process b) according to the invention.

The diborane derivatives additionally required as starting substances for carrying out the process c) according to the invention are generally defined by the formula (VI). In this formula (VI) G³ and G⁴they preferably represent respectively methyl, ethyl, propyl, butyl or together tetramethylethylene.

The diborane derivatives of formula (VI) are generally known synthetic chemicals.

The halogenobenzene derivatives required as starting substances for carrying out the process c) according to the invention are generally defined by the formula (VII). In this formula (VII) R¹ represents chlorine or methyl. X³ it preferably represents bromine, iodine or trifluoromethylsulfonyloxy.

The halogenobenzene derivatives of formula (VII) are generally known chemicals.

Suitable diluents for carrying out process a) according to the invention are all inert organic solvents. These preferably include aliphatic, alicyclic or aromatic hydrocarbons, such as, for example, petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin; halogenated hydrocarbons such as, for example, chlorobenzene, dichlorobenzene, dichloromethane, chloroform, tetrachloromethane, dichloroethane or trichloroethane; ethers such as diethyl ether, diisopropylether, methyl-t-butyl ether, methyl-t-amylether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane or anisole or amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric acid triamide.

The process a) according to the invention is carried out optionally in the presence of a suitable acid acceptor. As such, all customary inorganic or organic bases are taken into account. These preferably include alkaline earth or alkali metal hydrides, hydroxides, amides, alcoholates, acetates, carbonates or hydrogen carbonates, such as, for example, sodium hydride, sodium amide, sodium methylate, sodium ethylate, potassium tert-butylate, hydroxide sodium, potassium hydroxide, ammonium hydroxide, sodium acetate, potassium acetate, calcium acetate, ammonium acetate, sodium carbonate, potassium carbonate, potassium hydrogen carbonate, sodium hydrogencarbonate or cesium carbonate, as well as tertiary amines such as trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, N, N-dimethylbenzylamine, pyridine, N-methylpiperidine, N-methylmorpholine, N, N-dimethylaminopyridine, diazabicycloCO diazabicilonene (DBN) or diazabicycloundecene (DBU).

The reaction temperatures can be varied in carrying out the process a) according to the invention over a wide range. In general, it works at temperatures from 0 ° C to 150 ° C, preferably at temperatures from 20 ° C to 110 ° C.

To carry out the process a) according to the invention for the preparation of compounds of formula (I), per mole of the pyrazolylcarboxylic acid halide of formula (II) is generally used 0.2 to 5 moles, preferably 0, 5 to 2 moles of aniline derivative of formula (III).

The diluent used for carrying out processes b) and c) according to the invention is all inert organic solvents. These preferably include aliphatic, alicyclic or aromatic hydrocarbons, such as, for example, petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin; ethers such as diethyl ether, diisopropylether, methyl-t-butyl ether, methyl-t-amylether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, or anisole; nitriles, such as acetonitrile, propionitrile, n- or i-butyronitrile, or benzonitrile; amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric acid triamide; esters such as acetic acid methyl ester or acetic acid ethyl ester; sulfoxides, such as dimethylsulfoxide; sulfones such as sulfolane; alcohols, such as methanol, ethanol, n- or i-propanol, n-, i-, s- or t-butanol, ethanediol, propan-1,2-diol, ethoxyethanol, methoxyethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, their mixtures with water or pure water.

The reaction temperatures can be varied in carrying out process b) and c) according to the invention over a wide range. In general, it works at temperatures from 0 ° C to 150 ° C, preferably at temperatures from 20 ° C to 110 ° C.

Processes b) and c) according to the invention are optionally carried out in the presence of a suitable acid acceptor. As such, all customary inorganic or organic bases are taken into account. These preferably include alkaline earth metal or alkali metal hydrides, hydroxides, amides, alcoholates, acetates, fluorides, phosphates, carbonates or hydrogen carbonates, such as, for example, sodium hydride, sodium amide, sodium diisopropylamide, sodium methylate, sodium ethylate, sodium tert-butylate, sodium hydroxide, potassium hydroxide, sodium acetate, potassium acetate, sodium phosphate, potassium phosphate, potassium fluoride, cesium fluoride, sodium carbonate, potassium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate or cesium carbonate, as well as tertiary amines such as trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, N, N-dimethylbenzylamine, pyridine, N-methylpiperidine, N -methylmorpholine, N, N-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclonone (DBN) or diazabicycloundecene (DBU).

ES 2 313 615 T3

Processes b) and c) are carried out according to the invention in the presence of a catalyst such as, for example, a palladium salt or complex. Palladium chloride, palladium acetate, tetrakis- (triphenylphosphine) palladium or 1,1'-bis (diphenylphosphino) ferrocenpalladium chloride or 1,1'-bis (diphenylphosphino) ferrocenepalladium chloride ( II).

A palladium complex can also be produced in the reaction mixture if a palladium salt and a complex ligand such as, for example, triphenylphosphane, tri-tert-butylphosphane, tricyclohexylphosphane, 2- (dicyclohexylphosphan) are separately added to the reaction. -biphenyl, 2- (di-tert-butylphosphan) -biphenyl, 2- (dicyclohexylphosphan) -2 '- (N, N-dimethylamino) -biphenyl, triphenylphosphane, tris- (o-tolyl) -phosphane, 3- (diphenylphosphino ) sodium benzenesulfonate, tris-2- (methoxyphenyl) -phosphane, 2,2'-bis- (diphenylphosphan) -1,1'-binaphthyl, 1,4-bis (diphenylphosphan) -butane, 1,2-bis- (diphenyl-phosphan) -ethane, 1,4-bis (dicyclohexylphosphan ) -butane, 1,2-bis- (dicyclohexylphosphan) -ethane, 2- (dicyclohexylphosphan) -2 '- (N, N-dimethylamino) -biphenyl, bis (diphenylphosphino) ferrocene or tris- (2,4-tert- butylphenyl) -phosphite.

To carry out process b) according to the invention, for the preparation of the compounds of formula (I), per mole of halogenopyrazolylcarboxanilide of formula (IV) is used in general from 1 to 15 moles, preferably from 1 to 5 moles in derivative boronic acid of formula (V).

To carry out process c) according to the invention for the preparation of compounds of formula (I), per mole of halogeopyrazolylcarboxanilide of formula (IV) is used in general from 1 to 15 moles, preferably from 1 to 5 moles of derivative of diborane of formula (VI) and 1 to 15 moles, preferably 1 to 5 moles of halogenobenzene derivative of formula (VII).

The processes a), b) and c) according to the invention are generally used under normal pressure. However, it is also possible to work at elevated or reduced pressure - generally between 10 kPa and 1000 kPa.

The substances according to the invention have a strong microbicidal effect and can be used to combat unwanted microorganisms such as fungi and bacteria, in the protection of plants and in the protection of materials.

Fungicides can be used in plant protection to combat plasmodiophoromycetes, oomycetes, chytridiomycetes, zygomycetes, ascomycetes, basidiomycetes, and deuteromycetes.

Bactericides can be used in plant protection to combat Pseudomonadaceae, Rhizobiaceae, Enterobacteriaceae, Corynebacteriaceae, and Streptomycetaceae.

By way of example, but not by way of limitation, it is worth mentioning some pathogens of fungal and bacterial diseases that are found in the terms mentioned above:

diseases caused by Echten Mehltaus pathogens, such as, for example, by Blumeria species, such as, for example, Blumeria graminis;

Podosphaera species, such as, for example, Podosphaera leucotricha;

Sphaerotheca species, such as Sphaerothecafuliginea;

Uncinula species, such as Uncinula necator;

diseases caused by rust disease pathogens, such as Gymnosporangium species, such as Gymnosporangium sabinae;

Hemileia species, such as Hemileia vastatrix;

Phakopsora species, such as Phakopsora pachyrhizi and Phakopsora meibomiae; Puccinia species, such as Puccinia recondita;

Uromyces species, such as Uromyces appendiculatus;

diseases caused by pathogens of the oomycete group, such as, for example, by Bremia species, such as, for example, Bremia lactucae;

Peronospora species, such as Peronospora pisi or P. brassicae;

Phytophthora species, such as Phytophthora infestans;

ES 2 313 615 T3 Plasmopara species, such as Plasmopara vitícola;

Pseudoperonospora species, such as, for example, Pseudoperonospora humuli or Pseudoperonospora cubensis;

Pythium species, such as Pythium ultimum;

dry fog and leaf wilting diseases caused for example by Alternaria species such as Alternaria solani;

Cercospora species, such as Cercospora beticola;

Cladiosporum species, such as Cladiosporium cucumerinum;

Cochliobolus species, such as Cochliobolus sativus (conidia forms: Drechslera, Sin: Helminthosporium);

Colletotrichum species, such as Colletotrichum lindemuthanium;

Cycloconium species, such as Cycloconium oleaginum; Diaporthe species, such as Diaporthe citri;

Elsinoe species, such as Elsinoe fawcettii;

Gloeosporium species, such as Gloeosporium laeticolor;

Glomerella species, such as Glomerella cingulata;

Guignardia species, such as Guignardia bidwelli;

Leptosphaeria species, such as Leptosphaeria maculans;

Magnaporthe species, such as Magnaporthe grisea;

Mycosphaerella species, such as Mycosphaerella graminicola;

Phaeosphaeria species, such as Phaeosphaeria nodorum;

Pyrenophora species, such as Pyrenophora teres;

Ramularia species, such as Ramularia collo-cygni;

Rhynchosporium species, such as Rhynchosporium secalis;

Septoria species, such as Septoria apii;

Typhula species, such as Typhula incarnata;

Venturia species, such as Venturia inaequalis;

root and stem diseases caused for example by Corticium species, such as Corticium graminearum;

Fusarium species, such as Fusarium oxysporum;

Gaeumannomyces species, such as Gaeumannomyces graminis;

Rhizoctonia species, such as Rhizoctonia solani;

Tapesia species, such as Tapesia acuformis;

Thielaviopsis species, such as Thielaviopsis basicola;

ear and panicle diseases (including corn ears) caused, for example, by Alternaria species, such as Alternaria spp .;

ES 2 313 615 T3 Aspergillus species, such as Aspergillus flavus;

Cladosporium species, such as Cladosporium spp .;

Claviceps species, such as Claviceps purpurea;

Fusarium species, such as Fusarium culmorum;

Gibberella species, such as Gibberella zeae;

Monographella species, such as Monographella nivalis;

diseases caused by ustilaginales, such as, for example, by Sphacelotheca species, such as, for example, Sphacelotheca reiliana;

Tilletia species, such as Tilletia caries;

Urocystis species, such as Urocystis occulta;

Ustilago species, such as Ustilago nuda;

fruit rot caused, for example, by Aspergillus species, such as, for example, Aspergillus flavus;

Botrytis species, such as Botrytis cinerea;

Penicillium species, such as Penicillium expansum;

seed rot and wilting, as well as seedling diseases, caused for example by Fusarium species, such as Fusarium culmorum;

Phytophthora species, such as Phytophthora cactorum;

Pythium species, such as Pythium ultimum;

Rhizoctonia species, such as Rhizoctonia solani;

Sclerotium species, such as Sclerotium rolfsii;

carcinogenic diseases, gills and knobby outgrowths, caused for example by Nectria species, such as Nectria galligena;

wilting diseases caused for example by Monilinia species, such as Monilinia laxa;

deformations of leaves, flowers and fruits caused, for example, by Taphrina species, such as Taphrina deformans;

degenerative diseases of woody plants caused, for example, by Esca species, such as Phaemoniella clamydospora;

flower and seed diseases caused, for example, by Botrytis species, such as Botrytis cinerea;

plant bulb diseases caused, for example, by Rhizoctonia species, such as Rhizoctonia solani;

ES 2 313 615 T3 diseases caused by bacterial pathogens, such as Xanthomonas species, such as Xanthomonas campestris pv. oryzae;

Pseudomonas species, such as, for example, Pseudomonas syringae pv. lachrymans;

Erwinia species, such as Erwinia amylovora;

Preferably the following soybean diseases can be fought:

fungal diseases on leaves, stems, pods and seeds, caused for example by Alternaria leaf spot (Alternaria spec. atrans tenuissima), anthracnose (Colletotrichum gloeosporoides dematium var. truncatum), brown spot (Septoria glycines), Cercospora leaf spot and blight (Cercospora kikuchii), Choanephora leaf blight (Choanephora infundibulifera trispora (Syn.)), Dactuliophora leaf blight (Dactuliophora glycines), Dactuliophora glycines (Dactuliophora glycines) beet (Peronospora manshurica), Drechslera blight (Drechslera glycini), frog-eye leaf spot (Cercospora sojina), Leptosphaerulina leaf spot (Leptosphaerulina trifolii), Phyllostica leaf spot (Phyllosticta sojaecola), cereal powdery mildew (Microsphaera diffusa), Pyrenochaeta leaf spot (Pyrenochaeta glycines), aerial rhizoctonia, foliage, and cobweb blight (Rhizoctonia solani), rust (Phakopsora pachyrnahizi), Sphaceloma glycines), Stemphylium leaf blight (Stemphylium botryosum), Target Spot (Corynespora cassiicola) fungal root and stem base diseases caused, for example, Black root rot (Calonectria crotalariae), charcoal rot (Macrophomina phaseolina), Fusarium blight or wilt, root rot, and pod and collar rot (Fusarium oxysporum, Fusarium orthoceras, Fusarium semitectum, Fusarium equiseti) , root rot by Mycoleptodiscus (Mycoleptodiscus terrestris), Neocosmospora (Neocosmopspora vasinfecta), sheath and trunk blight (Diaporthe phaseolorum), trunk cancer (Diaporthe phaseolorum var. caulivora), Phytophthora rot (Phytophthora megasperma), brown stem rot (Phialophora gregata), Pythium rot (Pythium aphanidermatum, Pythium irregulare, Pythium debaryanum, Pythium myriotylum, Pythium ultizoimum root rot) , and seedling disease (Rhizoctonia solani), Sclerotinia stem rot (Sclerotinia sclerotiorum), Sclerotinia Southern blight (Sclerotinia rolfsii), Thielaviopsis root rot (Thielaviopsis basicola).

The active principles according to the invention also have a strong reinforcing effect on plants. These are therefore suitable for mobilizing the plant's own defense forces against infestation by unwanted microorganisms.

By plant reinforcing substances (inducing resistance) it is understood in this respect those substances which can stimulate the defense system of plants such that the treated plants in subsequent inoculation with unwanted organisms develop resistance against these microorganisms.

By unwanted microorganisms, we mean phytopathogenic fungi, bacteria and viruses. The substances according to the invention can therefore be used to protect plants in a desired period of time after treatment against infestation by the harmful pathogens mentioned. The period of time within which this protection develops generally extends from 1 to 10 days, preferably 1 to 7 days after treatment of the plants with the active principles.

The good tolerance by the plants of the active principles in the concentrations necessary to combat plant diseases allows a treatment of parts of aerial plants, of plants and seeds and of the soil.

In this connection, the active ingredients according to the invention can be used with particularly good success in combating cereal diseases, for example against Puccinia species and diseases in wine, fruit and vegetable crops, such as, for example, against Botrytis, Venturia or Alternaria species.

The active principles according to the invention are also suitable for increasing the yield of the crop. These are also low toxicity and have good compatibility with plants.

The active compounds according to the invention can optionally be used in certain concentrations and application amounts also as herbicides, to influence the growth of plants as well as to combat animal parasites. These can optionally be used as intermediates and pre-products for the synthesis of other active ingredients.

According to the invention, all plants and plant parts can be treated. By plants are understood, in this regard, all plants and plant populations, such as desired and unwanted wild plants or crop plants (including naturally occurring crop plants). The crop plants can be plants that can be obtained by conventional selection and optimization procedures or by biotechnological and genetic technology procedures or combinations of these procedures, including transgenic plants and including

ES 2 313 615 T3 plant species protectable by the right to protect varieties or non-protectable plant varieties. Plant parts should be understood as all the aerial and subterranean parts and organs of the plant, such as bud, leaf, flower and root, citing for example leaves, needles, stems, trunks, flowers, fruiting bodies, fruits and seeds, as well as roots. , tubers and rhizomes. Crop products as well as vegetative and generative propagation material, for example cuttings, tubers, rhizomes, layers and seeds, belong to the plant parts.

The treatment according to the invention of plants and plant parts with the active ingredients is carried out directly or by exposure to their environment, living space or storage space according to the usual treatment procedures, for example by immersion, spraying, spraying, vaporization, nebulization, dispersion, spreading, pouring and in reproductive material, especially in seeds, also by means of single or multi-layer envelopes.

In the protection of materials, the substances according to the invention can be used for the protection of industrial materials against infestation and destruction by unwanted microorganisms.

By industrial materials are understood as far as the present invention is concerned, lifeless materials, which can be produced for use in industry. For example, they can be industrial materials that should be protected by active principles according to the invention before microbial change or destruction, adhesives, glues, paper and cardboard, textiles, leather, wood, paints and plastic articles, cooling lubricants and other materials, which can be infested or decomposed by microorganisms. Within the framework of the materials to be protected, it is also worth mentioning part of production facilities, for example cooling water circuits, which can be harmed by the multiplication of microorganisms. Within the framework of the present invention, mention should be made as industrial materials of preferably plastics, glue, papers and cardboard, leather, wood, paint, cooling lubricants and heat transfer fluids, especially wood.

As microorganisms that can cause decomposition or change of industrial materials, mention may be made of, for example, bacteria, fungi, yeasts, algae and mucilaginous organisms. Preferably the active principles according to the invention act against fungi, especially mucilaginous fungi, fungi that color wood and destroy wood (basidiomycetenes) as well as against mucilaginous organisms and algae.

Mention should be made, for example, of microorganisms of the following genera:

I would alternate like I would alternate tenius,

Aspergillus as Aspergillus niger,

Chaetomium as Cahetomium Globosum,

Coniphora as Coniophora puetana,

Lentinus as Lentinus tigrinus,

Penicillium as Penicillium glaucum,

Polyporus like Polyporus versicolor,

Aureobasidium as Aureobasidium pullulans,

Sclerophoma like Sclerophoma pityophila,

Trichoderma as Trichoderma viride,

Escherichia as Escherichia coli,

Pseudomonas as, Pseudomonas aeruginosa,

Staphylococcus such as Staphylococcus aureus.

The active principles can be transformed according to their respective physical and / or chemical properties into the usual formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, microencapsulations in polymeric substances and in seed wrapping masses. , as well as hot and cold ULV mist formulations.

These formulations are prepared in a known way, for example, by mixing the active ingredients with diluents, thus liquid solvents, with gases liquefied under pressure and / or solid carriers, optionally with the use of surfactants, hence emulsifying agents and / or dispersants and / or foaming agents. When using water as diluent, for example organic solvents can also be used as builders. As solvents

ES 2 313 615 T3 liquids are essentially taken into account: aromatic compounds, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatic compounds and chlorinated aliphatic hydrocarbons, such as chlorobenzene, chloroethylene or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, alcohols, such as butanol or glycol as well as their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulfoxide, as well as water. By diluents or carriers in the form of liquefied gas are meant those liquids which are in the form of gas at normal temperature and normal pressure, for example propellant gases for aerosols, such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide. As solid carriers the following are considered: for example, natural rock powders, such as kaolin, alumina, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and synthetic rock powders, such as highly dispersed silicic acid, aluminum oxide and silicates. As solid carriers for granules the following are considered: for example: broken and fractionated natural rocks such as calcite, marble, pumice stone, sepiolite, dolomite as well as synthetic granules of inorganic and organic powders as well as granules of organic material such as sawdust, coconut shell , ears and stems of tobacco. Examples of emulsifying and / or foaming agents include: for example, non-ionogenic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates , aryl sulfonates as well as albumin hydrolysates. The following are considered dispersants: for example, lignin sulphite bleaches and methylcellulose.

They can be used in adhesive formulations such as carboxymethylcellulose, natural and synthetic polymers in powder, grain or latex form, such as acacia, polyvinyl alcohol, poly (vinyl acetate), as well as natural phospholipids such as cephalin and lecithin and phospholipids synthetics. Other additives can be mineral and vegetable oils.

Dyes such as inorganic pigments can be used, for example, iron oxide, titanium oxide, ferrocyanide blue and organic dyes such as alizarin, azo and metallic phthalocyanine dyes and oligonutrients such as iron, manganese, boron, copper, cobalt salts, molybdenum and zinc.

The formulations generally contain between 0.1 and 95% by weight of active principle, preferably between 0.5 and 90%.

The active principles according to the invention can be used as such or in their formulations also in admixture with known fungicides, bactericides, acaricides, nematicides or insecticides, to broaden the spectrum of activity or reduce resistance developments. In many cases, synergistic effects are obtained in this regard, ie the activity of the mixture is greater than the activity of the individual components.

As mixing partners, for example, the following compounds are taken into account:

Fungicides

1) Inhibitors of nucleic acid synthesis: eg benalaxyl, benalaxyl-m, bupyrimate, clozylacon, dimethyrimol, etyrimol, furalaxyl, hymexazole, mephenoxam, metalaxyl, metalaxyl-m, ofurace, oxadixyl, oxolinic acid

2) Mitosis and cell division inhibitors: eg, benomyl, carbendazim, dietofencarb, ethaboxam, fuberidazole, pencycuron, thiabendazole, thiophanate-methyl, zoxamide;

3) Respiration inhibitors (respiratory chain inhibitors):

3.1) Inhibitors of complex I of the respiratory chain: for example, diflumetorim

3.2) Inhibitors of complex II of the respiratory chain: for example, boscalid / nicobifene, carboxin, fenfuram, flutolanil, furametpir, mepronil, oxycarboxin, penthiopyrad, thifluzamide;

3.3) Inhibitors of complex III of the respiratory chain: for example, amisulbrom, azoxystrobin, ciazofamid, dimoxystrobin, enestrobin, famoxadon, fenamidone, fluoxastrobin, cresoxim-methyl, metominostrobin, orisastrobin, pyraclostrobin, picoxystrobin, triphloxystrobin

4) Decouplers: for example, dinocap, fluazinam, meptildinocap;

5) Inhibitors of ATP production: eg, fentinacetate, fentina chloride, fentina hydroxide, silthofam;

6) Inhibitors of amino acid and protein biosynthesis: eg, andoprim, blasticidin-s, cyprodinil, casugamycin, casugamycin hydrochloride hydrate, mepanipyrim, pyrimethanil;

7) Inhibitors of signal transduction: eg, fenpiclonil, fludioxonilium, quinoxyphene;

8) Inhibitors of fat and membrane synthesis: for example, biphenyl, chlozolinate, ediphenphos, iodocarb, iprobenphos, iprodione, isoprothiolane, procymidone, propamocarb hydrochloride, pyrazofos, tolclofos-methyl, vinclozolin;

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9) Ergosterol biosynthesis inhibitors: for example, aldimorf, azaconazole, bitertanol, bromuconazole, cyproconazole, diclobutrazol, difenoconazole, diniconazole, diniconazole-m, dodemorf, dodemorph acetate, epoxiconazole, ethaconazole, fenarimol, fenbuconazole, fehexamide, fenimpholorphidine, fenbuquinidimconazole, fenimpholorphidine, phenolimorphyl propridine , furconazole, furconazole-cis, hexaconazole, imizalil, imizalyl sulfate, imibenconazole, ipconazole, metconazole, myclobutanil, naftifine, nuarimol, oxpoconazole, paclobutrazol, pefurazoate, penconazole, prochloraz, propiconazole, prothioconazole, pyributicarb, pyrifenox, simeconazole, spiroxamine, tebuconazole, terbinafine, tetraconazole, triadimefone, triadimenol, tridemorph, triflumizole, triforine, triticonazole, uniconazole, vor viniconazole;

10) Inhibitors of cell wall synthesis: eg, benthiavalicarb, dimethomorf, flumorf, iprovalicarb, polyoxins, polyoxorim, validamycin A;

11) Melanin biosynthesis inhibitors: eg capropamide, diclocymeth, phenoxanil, phthalide, pyroquilone, tricyclazole;

12) Resistance inducers: eg acibenzolar-S-methyl, probenazole, thiadinyl;

13) Compounds with multisite activity: eg Bordeaux mixture, captafol, captane, chlorothalonil, copper naphthenate, copper oxide, copper oxychloride, copper preparations such as copper hydroxide, copper sulfate, diclofluanid, dithianone, dodine, dodine free base , ferbam, fluorofolpet, folpet, guazatine, guazatine acetate, iminoctadin, iminoctadine albesylate, iminoctadine triacetate, manganese-copper, mancozeb, maneb, methiram, methyram zinc, oxine-copper, propineb, sulfur and sulfur preparations such as, for example, calcium polysulfide, thiram, tolylfluanide, zineb, ziram;

12) A compound from the following list: (2E) -2- (2 - {[6- (3-chloro-2-methylphenoxy) -5-fluoropyrimidin-2-yl] oxy} phenyl) -2 (methoxyimino) -N-methylacetamide, (2E) -2 - {2 - [({[(1E) -1- (3 - {[(E) -1-fluoro-2-phenylvinyl] oxy} phenyl) ethylidene] amino} oxy) methyl] phenyl} -2 (meteoxyimino) -N-methylacetamide, 1- (2-chlorophenyl) -2- (1H-1,2,2-triazol-1-yl) cycloheptanol, 1 - [(2-methoxyphenoxy) methyl] -2,2-dimethylpropyl-1H -imidazole-1-carboxylate, 2- (2-chlorophenyl) -N- {2- [3-methoxy-2- (prop-2-y-1-yloxy) phenyl] ethyl} -2- (prop-2- in-1-yloxy) acetamide, 2,3,5,6-tetrachloro-2- (methylsulfonyl) pyridine, 2-butoxy-6-iodo-3-propyl-2H-chromen-2-one, 2-chloro-N- (1,1,3-trimethyl- 2,3-dihydro-1H-inden-2-yl) nicotinamide, 2-phenylphenol and salts thereof, 3,2,5-trichloropyridine-2,6-dicarbonitrile, 3,2-dichloro-N- (2- Cyanophenyl) isothiazole-5-carboxamide, 3- [5- (2-chlorophenyl) -2,3-dimethylisoxazolidin-3-yl] pyridine, 5-chloro-6- (2,2,6-trifluorophenyl) -N - [(1R ) -1,2,2-trimethylpropyl] [1,2,2] triazolo [1,5-a] pyrimidin-7-amine, 5-chloro-7- (2-methylpiperidin-1-yl) -6- (2,2,6-trifluorophenyl) [1,2,2] triazolo [1,5-a] pyrimidine, 5-chloro-N [ (1R) -1,2-dimethylpropyl] -6- (2,2,6-trifluorophenyl) [1,2,2] triazolo [1,5-a] pyrimidin-7-amine, 8-hydroxyquinoline sulfate, benthiazole, betoxazine , capsimycin, carvone, quinomethionate, cufraneb, ciflufenamid, cymoxanil, dazomet, debacarb, dichloroofen, diclomezine, dichloran, difenzoquat, diphenylamine methylsulfate, ferimzone, flumetover, fluopimicolide, flusoroulfide, fluoroulfide fosetyl-aluminum, fosety-calcium, fosetyl-sodium, hexachlorobenzene, irumamycin, metasulfocarb, (2-chloro-5 - {(1E) N - [(6-methylpyridin-2-yl) methoxy] ethanimidoyl} benzyl) methyl carbamate Methyl, (2E) -2 {2 - [({cyclopropyl [(2-methoxyphenyl) imino] methyl} thio) methyl] phenyl} -3-methoxy-acrylate, 1- (2,2-dimethyl-2,3 methyl -dihydro1H-inden-1-yl) -1H-imidazole-5-carboxylate, methyl 3- (2-chlorophenyl) -3 - {[N- (isopropoxycarbonyl) valyl] amino} propanoate, methyl isothiocyanate, methaphenone , downy mildew, N- (3 ', 2'-dichloro-5-fluorobiphenyl-2-yl) -3- (difluoromethyl) -1-methyl-1H-pyrazole-2-carboxamide, N- (3-ethyl-3,5,5 -trimethylcyclohexyl) -3- (formylamino) -2-hydroxybenzamide, N (2-chloro-2-nitrophenyl) N-ethyl-2-methylbenzenesulfonamide, N - [(5-bromo-3-chloropyridin-2-yl) methyl] -2,2-dichloronicotinamide, N- [1- (5-bromo-3-chloropyridin-2-yl) ethyl] -2,2-dichloronicotinamide, N- [1- (5-bromo-3-chloropyridin-2- yl) ethyl] -2-fluoro2-iodnicotinamide, N- [2- (2 - {[3- (2-chlorophenyl) prop-2-in-1-yl] oxy} -3-methoxyphenyl) ethyl] -N² - (methylsulfonyl) valinamide, N {(Z) - [(cyclopropylmethoxy) imino] [6- (di-fluoromethoxy) -2,3-difluorophenyl] methyl} -2-phenylacetamide, N- {2- [3-chloro- 5- (trifluoromethyl) pyridin-2-yl] ethyl} -2- (trifluoromethyl) benzamide, natamycin, nickel dimethyldithiocarbamate, nitrotalisopropyl, O- {1 - [(2-methoxyphenoxy) methyl] -2,2-dimethylpropyl} 1H -Imidazole-1-carbothioate, octilinone, oxamocarb, oxyphenthiine, pentachlorophenol and salts, phosphoric acid and its salts, piperaline, propamocarb, fosethylate, propanosine-sodium, proquinazid, Pyrrolnitrine, Quintozene, Tecloftalam, Technazene, Triazoxide, Triclamide, Zarylamide.

Bactericides bronopol, dichlorophene, nitpyrine, nickel dimethyldithiocarbamate, kasugamycin, octilinone, furancarboxylic acid, oxytetracycline, probenazole, streptomycin, tecloftalam, copper sulfate and other copper preparations.

Insecticides / acaricides / nematicides

1. Acetylcholinesterase (AChE) inhibitors

1.1 Carbamates (for example, alanicarb, aldicarb, aldoxycarb, alixicarb, aminocarb, azamethiphos, bendiocarb, benfuracarb, bufencarb, butacarb, butocarboxim, butoxycarboxim, carbaryl, carbofuran, carbosulfan, chloethophos, cyanobuophos, cyanobenophosenoboshen phenothiocarb, formethanate, furathiocarb, isoprocarb, metam-sodium, methiocarb, methomyl, metolcarb, oxamyl, pyrimicarb, promecarb, propoxur, thiodicarb, thiophanox, triazamate, trimetacarb, XMC, xylylcarb)

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1.2 Organophosphates (for example, acefate, azamethiphos, azinphos (-methyl, -ethyl), bromophos-ethyl, bromo-fenvinphos (-methyl), butathiophos, cadusaphos, carbophenothione, chlorethoxyphos, chlorophenvinphos, chloromephos, chlormeopyrifos () , coumaphos, cyanophenophos, cyanophos, chlorophenvinphos, demeton-S-methyl, demeton-S-methylsulfone, dialiphos, diazinone, diclofentione, dichlorovos / DDVP, dicrotphos, dimethoate, dimethylvinphos, dioxabenzophos, EPN, europhosthiona, etymhophosthione , fenamiphos, fenitrothione, phensulfothione, fenthione, flupirazophos, phonophos, formothione, phosmethylan, fostiazate, heptenophos, iodophenphos, iprobenphos, isazophos, isophenphos, isopropyl o-salicylate, isoxationa, malathiophos, mecarvinphoside, methacryphoside, mecarvinphoside, metacryphionophoside omethoate, oxydemeton-methyl, parathiona, (-methyl / -ethyl), phentoate, phorate, fosalone, phosmet, phosphamidone, phosphocarb, foxim, pirimiphos (-methyl / -ethyl), phosphenophos, propaphos, propetamphos, protiophos, protoate, pyraclphos, pyridaphenthione, pyridathione, quinalphos, sebufos, sulfotep, sulprofos, tebupyrimphos, temephos, terbuphos, tetrachlorovinphos, thiometone, triazophos, trichlorophone, vamidothione)

2. Voltage Dependent Sodium Channel Modulators / Blockers

2.1 Pyrethroids (for example, acrinathrin, allethrin, (d-cis-trans, d-trans), beta-cyfluthrin, bifenthrin, bioalethrin, bioalethrin-S-cyclopentyl isomer, bioethanomethrin, biopermethrin, bioresmethrin, clovaportrin, cis-cypermethrin, cis-resmethrin, cis-permethrin, clocitrin, cycloprothrin, cyfluthrin, cyhalothrin, cypermethrin (alpha-beta-, theta-, zeta-), cyphenothrin, DDT, deltamethrin, empenthrin (1R isomer), sphen-valerate, etofenprox, fenflutrin fenpropathrin, fenpyritrine, fenvalerate, flubrocitrinate, flucitrinate, flufenprox, flumethrin, fluvalinate, fubfenprox, gamma-cyhalothrin, imiprotrin, cadethrin, lambda-cyhalothrin, metofluthrin, permethrin (cis-, trans-), phenothrin (isomer, 1R-protrothrin-protrine) , pyresmethrin, resmethrin, RU 15525, silafluofen, tau-fluvalinate, tefluthrin, teralethrin, tetramethrin (1R isomer); tralomethrin, transfluthrin, ZXI 8901, pyrethrins (pyrethrum))

2.2 Oxadiazines (for example, indoxacarb)

3. Acetylcholine receptor agonists / antagonists

3.1 Chloronicotinil / neonicotinoids (e.g. acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram, nitiazine, thiacloprid, thiamethoxam)

3.2 Nicotine, bensultap, cartap

Four. Acetylcholine receptor modulators

4.1 Spinosyns (e.g. spinosad)

5. GABA-controlled chloride channel antagonists

5.1 Cyclodieneorganochlor (e.g. camphechlor, chlordane, endosulfan, gamma-HCH, HCH, heptachlor, lindane, methoxychlor)

5.2 Fiproles (eg acetoprol, ethiprole, fipronil, vaniliprole)

6. Chloride channel activators

6.1 Mectins (for example, abamectin, avermectin, emamectin, emamectin benzoate, ivermectin, milbemectin, milbemycin)

7. Juvenile hormone mimics, (eg, diophenolan, epphenonane, fenoxycarb, hydroprene, cynoprene, methoprene, pyriproxyphene, triprene)

8. Ecdyson agonists / disruptors

8.1. Diacylhydrazines (eg, chromafenozide, halofenozide, methoxyphenozide, tebufenozide)

9. Chitin biosynthesis inhibitors

9.1 Benzoylureas (for example, bistrifluron, clofluazuron, diflubenzuron, fluazuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, penfluron, teflubenzuron, triflumuron)

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9.2 Buprofezine

9.3 Cyromazine

10. Oxidative phosphorylation inhibitors, ATP disruptors

10.1 Diafentiuron

10.2 Organotin compounds (eg azocyclotin, cyhexatin, fenbutatin oxides)

eleven. Decouplers of oxidative phosphorylation by disruption of the proton H gradient

11.1 Pyrroles (eg chlorophenapyr)

11.2 Dinitrophenols (eg, binapacirl, dinobuton, dinocap, DNOC)

12. Electron transport inhibitors part I

12.1 METT (eg, phenazaquine, fenpyroximate, pyrimidifen, pyridaben, tebufenpyrad, tolfenpyrad)

12.2 Hydramethylnon

12.3 Dicofol

13. Electron transport inhibitors part II

13.1 Rotenones

14. Electron transport inhibitors part III

14.1 acequinocyl, fluacripirim

fifteen. Microbial disruptors of the gut membrane of insects

Bacillus thuringiensis strains

16. Fat biosynthesis inhibitors

16.1 tetronic acids (eg spirodiclofen, spiromesifene)

16.2 tetramic acids [e.g. 3- (2,5-dimethylphenyl) -8-methoxy-2-oxo-1-azaspiro [4.5] dec-3-en4-ylethyl (aka 3- (2,5 -dimethylphenyl) -8-methoxy-2-oxo-1-azaspiro [4.5] dec-3-en-4-ylethyl of carbonic acid, CAS registry number: 382608-10-8) and ester cis-3- (2 , 5-dimethylphenyl) -8-methoxy-2-oxo-1-azaspiro [4.5] carbonic acid dec-3-en-4-ylethyl (CAS registry number: 203313-25-1)]

17. Carboxamides (for example, flonicamide)

18. Octopamine agonists (eg, amitraz)

19. Magnesium-stimulated ATPase inhibitors (eg, propargite)

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twenty. Phthalamides (for example, N² - [1,1-dimethyl-2- (methylsulfonyl) ethyl] -3-iodo-N¹ - [2-methyl-4- [1,2,2,2-tetrafluoro-1- (trifluoromethyl) ethyl] phenyl] -1,2-benzenedicarboxamide (CAS registry number: 272451-65-7), flubendiamide)

twenty-one. Nereistoxin analogs (eg, thiocyclam hydrogen oxalate, triosultap-sodium)

22. Biological compounds, hormones, or pheromones (for example, Azadirachtin, Bacillus spec., Beauveria spec., Codlemona, Metarrhizium spec., Paecilomyces spec., Thuringiensina, Verticillium spec.)

2. 3. Active principles with unknown or non-specific mechanisms of action

23.1 Fumigants (for example, aluminum phosphide, methyl bromide, sulfuryl fluoride)

23.2 Selective anti-nutrients (eg cryolite, flonicamid, pymetrozine)

23.3 Mite growth inhibitors (eg, clofetezine, ethoxazole, hexythiazox)

23.4 Amidoflumet, benclothiaz, benzoximate, biphenazate, bromopropylate, buprofezine, quinomethionate, chlorodimeform, chlorobenzilate, chloropicrin, clothiazoben, cycloprene, cyflumethophene, dicyclanyl, phenoxamylate, fentriphanyl, fluubenossineziminyl, fluubenossin, gupheniazimethyl, fluubenossin, fentriphenylmethyl, fluubenossin piperonyl, potassium oleate, pyrafluprole, pyridyl, pyriprole, sulfluramide, tetradiphon, tetrasul, triaratene, verbutin, in addition to the compound 3-methyl-phenyl-propylcarbamate (Tsumacida Z), the compound 3- (5-chloro-3-pyridinyl) -8- (2,2,2-trifluoroethyl) -8-azabicyclo [3.2.1] octan-3 -carbonitrile (CAS registry number 185982-80-3) and the corresponding 3-endo isomers (CAS registry number: 185984-60-5) (see WO 96/37494, WO 98/25923), as well as preparations containing insecticidal plant extracts, nematodes, fungi or viruses.

A mixture with other active ingredients known as herbicides or with fertilizers and growth regulators, protectors or semi-chemicals is also possible.

Furthermore, the compounds of formula (I) according to the invention also have very good antifungal effects. They have a wide spectrum of antifungal activity, especially against dermatophytes and blastomycetes, molds and diphasic fungi (for example, against Candida species such as Candida albicans, Candida glabrata) as well as Epidemophyton floccosum, Aspergillus species such as Aspergillus niger and Aspergillus fumigatus, species of Trichophyton such as Trichophyton mentagrophytes, microsporon species such as Microsporon canis and audouinii. The enumeration of these fungi does not represent in any way a limitation of the mycotic spectrum that can be covered, but is only for clarification.

The active ingredients can be applied as such, in the form of their formulations or the application forms prepared therefrom, as solutions, suspensions, sprays, pastes, soluble powders, dusting agents and ready-to-use granules. The application is carried out in the usual way, for example, by pouring, spraying, atomizing, dispersing, dusting, foaming, painting and the like. It is also possible to spread the active principles according to the ultra-low volume method or inject the active principle preparation or the active principle itself into the soil. Plant seeds can also be treated.

In the use of the active principles according to the invention as fungicides, the application rates can be varied according to each type of application within a wide range. In the treatment of plant parts, the application rates of active principle are generally between 0.1 and 10,000 g / ha, preferably between 10 and 1,000 g / ha. In the treatment of seeds, the application amounts of the active principle are generally between 0.001 and 50 g per kilogram of seed, preferably between 0.01 and 10 g per kilogram of seed. In soil treatment, the application rates of the active principle are generally between 0.1 and 10,000 g / ha, preferably between 1 and 5,000 g / ha.

As already mentioned above, all plants and their parts can be treated according to the invention. In a preferred embodiment, plant species and plant varieties of wild origin or obtained by conventional biological cultivation procedures, such as crossing or fusion of protoplasts, as well as their parts, are treated. In a further preferred embodiment, transgenic plants and plant varieties obtained by means of genetic technology methods are treated, where appropriate in combination with conventional processes (genetically modified organisms) and their parts. The term "parts" or "plant parts" was clarified above.

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In a particularly preferred manner, plants according to the invention of respectively commercial or in-use plant species are treated. By plant species, we mean plants with new properties ("traits"), which are bred either by conventional cultivation, by mutagenesis or by recombinant DNA techniques. These can be varieties, races, biotypes and genotypes.

Depending on the plant species or plant varieties, their habitat and growing conditions (soil, climate, vegetative period, feeding), superadditive ("synergistic") effects may also appear by the treatment according to the invention. Thus, for example, reduced application rates and / or broadening of the spectrum of action and / or a strengthening of the effect of the substances and agents that can be used according to the invention, better plant growth, greater tolerance to high o low temperatures, greater tolerance to drought or to the content of water or soil salts, higher flowering yield, easier harvesting, acceleration of maturation, higher harvest yields, higher quality and / or higher nutritional value of harvest products, greater storage capacity and / or processability of harvest products, which exceed the effects that are actually expected.

The preferred transgenic plants or plant varieties according to the invention for treating (obtained by genetic engineering) belong to all plants which by means of genetic engineering have obtained genetic material that confers on these plants especially advantageous valuable properties ("traits"). Examples of these properties are better plant growth, high tolerance to high or low temperatures, increased tolerance to dryness or to the salt content of water or soil, high flowering yield, easier harvesting, acceleration of maturation, higher yields. of harvest, higher quality and / or greater nutritional value of harvest products, greater storage capacity and / or processability of harvest products. Additional and especially outstanding examples of said properties are a high defense of plants against animal and microbial pests, such as against insects, mites, phytopathogenic fungi, bacteria and / or viruses, as well as a high tolerance of plants against certain principles. herbicidal actives. As examples of transgenic plants, important crop plants such as cereals (wheat, rice), corn, soybeans, potatoes, cotton, tobacco, rapeseed, as well as fruit plants (with the fruits apple, pear, citrus fruits and grapes of wine), especially corn, soybeans, potatoes, cotton, tobacco and rapeseed. As properties ("traits"), the high defense of plants against insects, arachnids, nematodes and snails, especially those toxins generated in plants by the genetic material of Bacillus thuringiensis (for example, by the CryIA genes) stand out. (a), CryIA (b), CryIA (c), CryIIA, CryIIIA, CryIIIB2, Cry9c Cry2Ab, Cry3Bb and CryIF, as well as their combinations) (hereinafter, "Bt plants"). As properties (“traits”), the high defense of plants against fungi, bacteria and viruses by means of systemic acquired resistance (SAR), sistemin, phytoalexins, triggers, as well as resistance genes and the corresponding proteins and toxins stand out. expressed. As properties ("traits"), the high tolerance of plants towards certain herbicidal active ingredients, for example imidazolinones, sulphonylureas, glyphosate or phosphinothricin (for example "PAT" gene), stands out in particular. Genes conferring the respectively desired properties ("traits") may also appear in combinations with each other in transgenic plants. Examples of "Bt plants" include corn varieties, cotton varieties, soybean varieties and potato varieties, which are marketed under the commercial references YIELD GARD^® (for example, corn, cotton, soybeans), KnockOut^® (for example, corn), StarLink^® (eg corn), Bollgard^® (cotton), Nucotn^® (cotton) and NewLeaf^® (potato). Examples of herbicide tolerant plants include corn varieties, cotton varieties, and soybean varieties that are marketed under the Roundup Ready trade references.^® (tolerance to glyphosate, eg corn, cotton, soy), Liberty Link^® (tolerance to phosphinothricin, eg rapeseed), IMI^® (tolerance to imidazolinones) and STS^® (tolerance against sulfonylureas, eg corn). As herbicide resistant plants (conventionally bred with herbicide tolerance), the varieties marketed under the reference Clearfield are also mentioned^® (for example, corn). Of course, these indications are also valid for plant varieties developed in the future or present on the future market with these or other genetic properties developed in the future ("traits").

The plants mentioned can be treated in a particularly advantageous manner according to the invention with the compounds of general formula I or the active ingredient mixtures according to the invention. The preferred ranges given above in the active ingredients or mixtures are also valid for the treatment of these plants. The treatment of plants with the compounds or mixtures mentioned especially in the present text is particularly noteworthy.

The preparation and use of the active principles according to the invention is clear from the following examples.

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Preparation examples

Example 1

<img file="ES2313615T3_D0011.tif" />

To a mixture consisting of 2.96 g (16.8 mmol) of 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid in 100 ml of dichloromethane, 1.6 ml of oxalic acid dichloride and 0.2 ml of dimethylformamide. After 2 hours at room temperature, a solution consisting of 3.83 g (16.0 mmol) of 4'-chloro-5.3'-difluorobiphenyl-2-yl-amine and 2.9 ml (20.8 mmol) in 100 ml of dichloromethane. The reaction mixture is stirred for 16 hours at room temperature. For work-up, the reaction mixture is added to water, the organic phase is separated, dried over magnesium sulfate and concentrated in vacuo. Column chromatography (petroleum ether / acetone 3: 1) gives 5.94 g (93% of theory) N- (4'-chloro-3,5-difluorobiphenyl-2-yl) -3- (difluoromethyl) -1-methyl-1H-pyrazole-4-carboxamide with logP (pH 2.3) = 3.05.

Analogously to Example 1 and according to the general test requirements in the description, the following compounds are obtained:

3-Difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid (5,3'-difluoro-4'-methyl-biphenyl-2-yl) -amide; log P (pH 2.3) = 3.05.

1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxylic acid (5,3'-difluoro-4'-methyl-biphenyl-2-yl) -amide log P (pH 2.3) = 3.27

1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxylic acid (4'-chloro-5,3'-difluoro-biphenyl-2-yl) -amide log P (pH 2.3) = 3.26

Preparation of starting substances of formula (III)

Example (III-1)

<img file="ES2313615T3_D0012.tif" />

In an atmosphere of protective gas, a mixture composed of 30.0 g (0.17 mol) of 4-chloro-3-fluorophenyl-boronic acid and 29.7 g (0.16 mol) of 2-bromo-4- is added. fluoroaniline in 170 ml of toluene and 17 ml of ethanol with 3.6 g (0.003 mol) of tetrakis (triphenylphosphin) palladium (0) and stirred for 16 hours at 80 ° C. After adding 200 ml of toluene and 200 ml of water, the organic phase is separated, dried over magnesium sulfate and concentrated in vacuo. Column chromatography (petroleum ether / acetone 4: 1) gives 26.1 g (70% of theory) of 4'-chloro-5,3'-difluorobiphenyl-2-yl-amine with log P (pH 2.3) = 3.18.

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Example (III-2)

Starting from 4-methyl-3-fluoro-phenylboronic acid and 2-bromo-4-fluoroaniline, the compound 5,3'-difluoro-4'-methyl-biphenyl-2- is obtained analogously to example (III-1). ylamine with log P (pH 2.3) = 2.94.

The determination of the log P values ​​given in the tables and subsequent preparation examples is carried out according to EU directive 79/831 annex V. A8 by HPLC (high performance liquid chromatography) on a reverse phase column (C 18 ), temperature: 43 ° C).

The determination is carried out in the acid range at pH 2.3 with 0.1% aqueous phosphoric acid and acetonitrile as eluents; linear gradient from 10% acetonitrile to 90% acetonitrile.

The calibration is carried out with unbranched alkan-2-ones (with 3 to 16 carbon atoms), whose log P values ​​are known (determination of the log P values ​​as a function of the retention times by linear interpolation between two successive alkanols ).

The maximum lambda values ​​were determined as a function of the UV spectra from 200 nm to 400 m at the maximums of the chromatographic signals.

Application examples

Example A

Botrytis (broad bean) test / protector

<td>Solvent:</td><td>24.5 parts by weight of acetone 24.5 parts by weight of dimethylacetamide</td>

<td>Emulsifier:</td><td>1 part by weight alkylaryl polyglycol ether</td>

To prepare a suitable active ingredient preparation, 1 part by weight of active ingredient is mixed with the given amounts of solvent and emulsifier and the concentrate is diluted with water to the desired concentration.

To test the protective activity, young plants are sprayed with the active ingredient preparation in the given application amount. After drying of the spray layer, 2 small pieces of agar covered with Botrytis cinerea are placed on each sheet. The inoculated plants are placed in a darkened chamber at approximately 20 ° C and 100% relative humidity.

days after inoculation, the size of the infestation spots on the leaves is assessed. In this respect 0% means a degree of effect corresponding to that of the control, while 100% means a degree of effect in which no infestation is observed.

(Table goes to next page)

ES 2 313 615 T3

TABLE A

<td colspan="6">Botrytis test (bean) / protector</td>

<td colspan="4">Active principle</td><td>Amount of application of active principle in ppm</td><td>Degree of effect on %</td>

<td>Known from</td><td colspan="2">document</td><td>WO</td><td></td><td></td>

<td colspan="2">03/070705 (example 10):</td><td></td><td></td><td> 100</td><td> 52</td>

<td></td><td>F</td><td></td><td></td><td></td><td></td>

<td></td><td></td><td></td><td></td><td></td><td></td>

<td> 0</td><td>ΓΪ1</td><td></td><td></td><td></td><td></td>

<td></td><td>Jl</td><td></td><td></td><td></td><td></td>

<td rowspan="2">* h</td><td>N</td><td></td><td></td><td></td><td></td>

<td>HI</td><td></td><td></td><td></td><td></td>

<td> /</td><td>rii</td><td></td><td></td><td></td><td></td>

<td>H₃C</td><td>l</td><td></td><td></td><td></td><td></td>

<td></td><td>F</td><td>^XCI</td><td></td><td></td><td></td>

<td>Known from</td><td colspan="2">document</td><td>wo</td><td></td><td></td>

<td colspan="2">03/070705 (example 12):</td><td></td><td></td><td> 100</td><td> 87</td>

<td></td><td></td><td>_XF</td><td></td><td></td><td></td>

<td>OR</td><td></td><td></td><td></td><td></td><td></td>

<td></td><td>Ace/</td><td></td><td></td><td></td><td></td>

<td>Lj</td><td>n Η I</td><td></td><td></td><td></td><td></td>

<td>z</td><td></td><td></td><td></td><td></td><td></td>

<td>h₃c</td><td>THE</td><td></td><td></td><td></td><td></td>

<td></td><td></td><td>Ci</td><td></td><td></td><td></td>

<td></td><td>F</td><td></td><td></td><td></td><td></td>

<td colspan="2">According to the invention:</td><td></td><td></td><td></td><td></td>

<td>or</td><td>THE</td><td>_XF</td><td></td><td> 100</td><td> 100</td>

<td></td><td rowspan="2">s AsA n γ^H i</td><td></td><td></td><td></td><td></td>

<td>&lt;jr</td><td></td><td></td><td></td><td></td>

<td>Ν '/</td><td>ril</td><td></td><td></td><td></td><td></td>

<td></td><td></td><td></td><td></td><td></td><td></td>

<td></td><td>Cl</td><td></td><td></td><td></td><td></td>

Example B

Pyrenophora teres (barley) assay / protector

To prepare a suitable active ingredient preparation, 1 part by weight of active ingredient is mixed with the given amounts of solvent and emulsifier and the concentrate is diluted with water to the desired concentration.

To test the protective activity, young plants are sprayed with the active ingredient preparation in the given application amount. After drying of the spray layer, the plants are sprayed with a conidia suspension of Pyrenophora teres. The plants remain 48 hours at 20 ° C and 100% relative humidity.

The plants are then placed in a greenhouse at a temperature of about 20 ° C and relative humidity of about 80%.

days after inoculation, the titration is carried out. In this respect 0% means a degree of effect corresponding to that of the control, while 100% means a degree of effect in which no infestation is observed.

ES 2 313 615 T3

TABLE B

<td colspan="7">Pyrenophora teres (barley) assay / protector</td>

<td colspan="5">Active principle</td><td>Amount of application of active principle in ppm</td><td>Degree of effect on %</td>

<td>Known from</td><td colspan="3">document</td><td>WO</td><td></td><td></td>

<td colspan="3">03/070705 (example 10):</td><td></td><td></td><td></td><td></td>

<td></td><td></td><td>F</td><td></td><td></td><td></td><td></td>

<td>F ^ Z or</td><td></td><td>r '</td><td>Ϊ]</td><td></td><td></td><td></td>

<td></td><td rowspan="2">Y H</td><td>kx</td><td>Y</td><td></td><td></td><td></td>

<td>^Nahj</td><td></td><td></td><td></td><td> 1000</td><td> 93</td>

<td> /</td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>HsC</td><td></td><td></td><td>Jl ^ Cl</td><td></td><td></td><td></td>

<td></td><td></td><td>F</td><td></td><td></td><td></td><td></td>

<td>Solvent:</td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>25 parts in</td><td colspan="2">weight</td><td>of</td><td>N, N-</td><td></td><td></td>

<td>dimethylacetamide</td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>Emulsifier:</td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>0.6 parts</td><td>in</td><td></td><td>weight</td><td>of</td><td></td><td></td>

<td colspan="2">alkylarylpolyglycol ether</td><td></td><td></td><td></td><td></td><td></td>

<td colspan="4">According to the invention:</td><td></td><td></td><td></td>

<td>r .f</td><td></td><td></td><td>,,F</td><td></td><td></td><td></td>

<td>Ρ-γ or</td><td></td><td></td><td>Item</td><td></td><td></td><td></td>

<td></td><td>'NH</td><td>k ^</td><td>II</td><td></td><td></td><td></td>

<td></td><td></td><td>rA</td><td></td><td></td><td> 1000</td><td> 100</td>

<td>HjC</td><td></td><td></td><td>n</td><td></td><td></td><td></td>

<td></td><td></td><td></td><td></td><td></td><td></td><td></td>

<td></td><td></td><td>Cl</td><td></td><td></td><td></td><td></td>

<td>Solvent:</td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>50 parts in</td><td colspan="2">weight</td><td>of</td><td>N, N-</td><td></td><td></td>

<td>dimethylacetamide</td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>Emulsifier:</td><td></td><td></td><td></td><td></td><td></td><td></td>

<td>1.0 part</td><td>in</td><td></td><td>weight</td><td>of</td><td></td><td></td>

<td colspan="2">alkylarylpolyglycol ether</td><td></td><td></td><td></td><td></td><td></td>

Example C

Erysiphe (barley) assay / protector

To prepare a suitable active ingredient preparation, 1 part by weight of active ingredient is mixed with the given amounts of solvent and emulsifier and the concentrate is diluted with water to the desired concentration.

To test the protective activity, young plants are sprayed with the active ingredient preparation in the given application amount.

After drying of the spray layer, the plants are dusted with spores of Erysiphe graminis f.sp. hordei.

ES 2 313 615 T3

The plants are then placed in a greenhouse at a temperature of approximately 20 ° C and a relative humidity of approximately 80% to promote the development of powdery mildew pustules.

days after inoculation, the titration is carried out. In this respect 0% means a degree of effect corresponding to that of the control, while 100% means a degree of effect in which no infestation is observed.

TABLE C

<td colspan="3">Erysiphe (barley) assay / protector</td>

<td>Active principle</td><td>Amount of application of active principle in PPm</td><td>Degree of effect in %</td>

<td>Known from WO 03/070705</td><td></td><td></td>

<td>(example 10):</td><td></td><td></td>

<td>F</td><td> 1000</td><td> 33</td>

<td>_ F JL</td><td></td><td></td>

<td>⁰ ιϊι</td><td></td><td></td>

<td></td><td></td><td></td>

<td>Nτ '</td><td></td><td></td>

<td>\ I heard</td><td></td><td></td>

<td>go fl</td><td></td><td></td>

<td>k JL</td><td></td><td></td>

<td>Cl F</td><td></td><td></td>

<td>Solvent:</td><td></td><td></td>

<td>25 parts by weight of N, Nd¡methylacetamide</td><td></td><td></td>

<td>Emulsifier:</td><td></td><td></td>

<td>0.6 part by weight of alkylaryl polyglycol ether</td><td></td><td></td>

<td>According to the invention:</td><td></td><td></td>

<td>_F F</td><td></td><td></td>

<td></td><td></td><td></td>

<td>vy ^h</td><td> 1000</td><td> 78</td>

<td>/ r π</td><td></td><td></td>

<td>k JL</td><td></td><td></td>

<td>F</td><td></td><td></td>

<td>Cl</td><td></td><td></td>

<td>Solvent:</td><td></td><td></td>

<td>50 parts by weight of N, Nd¡methylacetamide</td><td></td><td></td>

<td>Emulsifier:</td><td></td><td></td>

<td>1.0 part by weight alkylaryl polyglycol ether</td><td></td><td></td>

ES 2 313 615 T3

Example D

Leptosphaeria nodorum (wheat) assay / protector

To prepare a suitable active ingredient preparation, 1 part by weight of active ingredient is mixed with the given amounts of solvent and emulsifier and the concentrate is diluted with water to the desired concentration.

To test the protective activity, young plants are sprayed with the active ingredient preparation in the given application amount. After drying of the spray layer, the plants are sprayed with a spore suspension of Leptosphaeria nodorum. The plants remain 48 hours at 20 ° C and 100% relative humidity in an incubation cabin.

The plants are then placed in a greenhouse at a temperature of about 15 ° C and a relative humidity of about 80%.

days after inoculation, the titration is carried out. In this respect 0% means a degree of effect corresponding to that of the control, while 100% means a degree of effect in which no infestation is observed.

TABLE D

<td colspan="3">Leptosphaeria nodorum (wheat) assay / protector</td>

<td>Active principle</td><td>Amount of application of active principle in PPm</td><td>Degree of effect in%</td>

<td>Known from WO 03/070705</td><td rowspan="2"> 1000</td><td rowspan="2"> 0</td>

<td>(example 10): F c X Ύ 3 ml \ I] HI Ν v L II and ci F Solvent: 25 parts by weight of N, N-dimethylacetamide Emulsifier: 0.6 part by weight of alkylaryl polyglycol ether</td>

<td>According to the invention:_F θ x 1 / ^H 1 'íA «₃c L II Cl Solvent: 50 parts by weight of N, Nd¡metalacetamide Emulsifier: 1.0 part by weight alkylaryl polyglycol ether</td><td> 1000</td><td> 84</td>