EP2049496A2

EP2049496A2 - 3-difluoromethylpyrazolylcarboxanilides

Info

Publication number: EP2049496A2
Application number: EP07801448A
Authority: EP
Inventors: Ralf Dunkel; Stefan Beeck; Jörg Nico Greul; Ulrike Wachendorf-Neumann; Peter Dahmen; Arnd Voerste
Original assignee: Bayer CropScience AG
Current assignee: Bayer CropScience AG
Priority date: 2006-08-03
Filing date: 2007-07-24
Publication date: 2009-04-22
Also published as: WO2008014905A2; WO2008014905A3; DE102006036222A1

Abstract

The invention relates to 3-difluoromethylpyrazolylcarboxanilides of the formula (I) in which the R1 radical is halogen, cyano, nitro, C1-C6-alkyl, C2-C6-alkenyl, C1-C4-alkoxy, C1-C4-alkylthio; C1-C4-alkylsulfonyl, C3-C6-cycloalkyl, or is C1-C4-haloalkyl, C1-C4-haloalkoxy, C1-C4-haloalkylthio or C1-C4-haloalkylsulfonyl having in each case from 1 to 5 halogen atoms, and to processes for their preparation and to their use for controlling undesired microorganisms.

Description

3-difluoromethyl-pyrazolylcarboxanilides

The invention relates to 3-difluoromethyl-pyrazolylcarboxanilide, and to processes for their preparation and their use for controlling unwanted microorganisms.

It is described in the prior art that many carboxanilides have fungicidal properties (see, for example, EP 0 545 099 and JP 9132567).

EP-A-0 589 301 teaches the fungicidal properties of N-bisphenyl- (1-methyl-3-difluoromethylpyrazol-4-yl) carboxamides in which the proximal phenyl ring of the biphenyl radical is unsubstituted.

EP-A-0 847 388 teaches the fungicidal properties of substituted N-bisphenyl (1,3-dimethyl-pyrazol-4-yl) carboxamides.

WO-A-05123690 teaches the fungicidal properties of N-bisphenyl- (1-methyl-3-difluoromethylpyrazol-4-yl) carboxamides in which the proximal phenyl ring is unsubstituted and the distal phenyl ring of the biphenyl radical is disubstituted.

The effectiveness of the substances described there is good, but leaves at low application rates in some cases to be desired.

There have now been new 3-difluoromethyl-pyrazolylcarboxanilides of the formula (I)

in which

R ¹ represents halogen, cyano, nitro, Ci-C _ö alkyl, C ₂ -C ₆ alkenyl, C ₁ -C ₄ -alkoxy, dC ₄ -alkylthio, Ci- C ₄ alkylsulfonyl, C ₃ -C ₆ - Cycloalkyl, or for C, -C ₄ -haloalkyl, Ci-C ₄ -haloalkoxy, C _r C ₄ haloalkylthio or Ci-C ₄ -haloalkylsulfonyl each having 1 to 5 halogen atoms, found.

It has furthermore been found that pyrazolylcarboxanilides of the formula (I) are obtained by reacting a) pyrazolylcarboxylic acid halides of the formula (II)

in which

X 'is halogen, with aniline derivatives of the formula (III)

in which

R ^{1 has} the meanings given above, or

b) Halogenpyrazolecarboxanilides of the formula (FV)

in which

X is bromine or iodine,

with boronic acid derivatives of the formula (V)

in which

R ^{1 has} the meanings given above,

G ¹ and G ^{2 are} each hydrogen or together are tetramethylethylene,

in the presence of a catalyst, or

c) Halogenpyrazolecarboxanilides of the formula (FV)

in which

X ^{2 is} bromine or iodine,

in a first step with a diborane derivative of the formula (VI)

G ⁴ - O ^ -G ⁴

B-B (VI)

₃ / \ ₃ G- O OG ³

in which G and G are each alkyl or together are alkanediyl,

in the presence of a catalyst and without working up in a second stage with halogenobenzene derivatives of the formula (VII)

in which

R ^{1 has} the meanings given above and

X ^{3 is} bromine, iodine or trifluoromethylsulfonyloxy,

in the presence of a catalyst, if appropriate in the presence of an acid binder and if appropriate in the presence of a diluent.

Finally, it has been found that the new 3-difluoromethyl-pyrazolylcarboxanilides of the formula (I) have very good microbicidal properties and can be used for controlling unwanted microorganisms both in crop protection and in the protection of materials.

Surprisingly, the 3-difluoromethyl-pyrazoIylcarboxanilide of the formula (I) according to the invention show a significantly better fungicidal activity than the constitutionally most similar, previously known active compounds of the same direction of action.

The pyrazolylcarboxanilides of the invention are generally defined by the formula (I).

Preferred are pyrazolylcarboxanilides of the formula (I) in which

R ^{1 is} fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, methylthio, ethylthio, n- or i- Propylthio, cyclopropyl, trifluoromethyl,

Trichloromethyl, trifluoroethyl, difluoromethoxy, trifluoromethoxy, difluorochloromethoxy, trifluoroethoxy, difluoromethylthio, difluorochloromethylthio or trifluoromethylthio., Particularly preferred are pyrazolylcarboxanilides of the formula (I) in which

R ^{1 is} fluorine, chlorine, bromine, methyl, trifluoromethyl, difluoromethoxy or trifluoromethoxy.

Very particular preference is given to pyrazolylcarboxanilides of the formula (I) in which R ^{1 is} chlorine.

The invention preferably relates to the compound of the formula (Ia)

Preferably the subject of the present invention is likewise the compound of the formula (Ib),

The present application relates in particular to compounds of the formula (I) in which

R ^{1 is} 4'-fluoro, 4-chloro, 4'-bromo, 4'-methyl, 4'-trifluoromethyl, 4'-difluoromethoxy or 4'-

Trifluoromethoxy stands.

The present application also relates in particular to compounds of the formula (I) in which

R ^{1 is} 3'-fluoro, 3'-chloro, 3'-bromo, 3'-methyl, 3'-trifluoromethyl, 3'-difluoromethoxy or 3'-trifluoromethoxy.

The general or preferred radical definitions listed above or

Explanations can also be made among each other, ie between the respective areas and Preferred areas can be combined as desired. They apply accordingly to the end products as well as to the precursors and intermediates. In addition, individual definitions can be omitted.

Saturated hydrocarbon radicals such as alkyl may also be used in conjunction with heteroatoms, e.g. in alkoxy, as far as possible, in each case straight-chain or branched.

Halogen substituted radicals, e.g. Haloalkyl, are halogenated one or more times to the maximum possible number of substituents. For multiple halogenation, the halogen atoms may be the same or different. Halogen is fluorine, chlorine, bromine or iodine, in particular fluorine, chlorine or bromine.

If, for example, 1-methyl-3- (trifluoromethyl) -1H-pyrazole-4-carbonyl chloride and 3'-chloro-5-fluoro-1, r-biphenyl-2-amine are used as starting materials and a base, the course of the process according to the invention a) are illustrated by the following scheme (I):

Scheme (I)

For carrying out the process a) required as starting materials 3-difluoromethyl-pyrazolylcarbonsäurehalogenide are generally defined by the formula (II).

The process a) can be carried out in the presence of a diluent and / or an acid binder.

The pyrazolylcarboxylic acid halides of the formula (II) are known and / or can be prepared by known processes (cf., for example, JP 01290662 and US 5,093,347).

The further required for carrying out the process a) according to the invention as starting materials

Aniline derivatives are generally defined by the formula (III). In this formula (III), R ^{1 is} preferably or particularly preferably those meanings which have already been mentioned in connection with the description of the compounds of the formula (I) according to the invention as being preferred or particularly preferred for these radicals. The aniline derivatives of the formula (III) are obtained by

d) fluorohaloanilines of the formula (VIII)

in which

X ^{2 has} the meaning given above,

with a boronic acid derivative of the formula (V)

in which

R ^{1 has} the meaning given above, and

G ¹ and G ^{2 are} each hydrogen or together are tetramethylethylene,

If, for example, 2-bromo-4-fluoroaniline and 3-chlorophenylboronic acid are used as starting materials and a base, the course of process d) according to the invention can be illustrated by the following scheme (II):

Scheme (II)

The Fluorhalogenaniline required for carrying out the process d) as starting materials are generally defined by the formula (VIII). In this formula (VIII), X ^{2 is} bromine or iodine.

The fluorohaloanilines of the formula (VIII) are known or can be obtained by known methods (see, for example, US-A-28939 or J. Org. Chem. 2001. 66, 4525-4542).

The boronic acid derivatives furthermore required for carrying out the process d) according to the invention as starting materials are generally defined by the formula (V). In this formula (V), R ^{1 is} preferably or particularly preferably those meanings which have already been mentioned in connection with the description of the compounds of the formula (I) according to the invention as being preferred or particularly preferred for R ¹ . G ¹ and G ² are each preferably hydrogen or together are tetramethylethylene.

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

Work-up to be further implemented.

If N- (2-bromo-4-fluorophenyl) -1-methyl-3- (difluoromethyl) -1H-pyrazole-4-carboxamide and 3-chlorophenylboronic acid are used as starting materials, and also a catalyst and a base, the Course of the process b) according to the invention by the following scheme (III): scheme

(III)

The halogen pyrazolecarboxanilides required as starting materials for carrying out the process b) according to the invention are generally defined by the formula (IV). In this formula (IV) X ^{2 are} preferably bromine or iodine.

The Halogenpyrazolcarboxanilide of formula (IV) are obtained by

e) pyrazolylcarboxylic acid halides of the formula (II)

in which

X ^{1 is} halogen, with

Fluorohalogenanilines of the formula (VIII)

in which

X ^{2 has} the meanings given above if appropriate in the presence of an acid binder and if appropriate in the presence of a Ver _¬ dünnungsmittels.

If, for example, 1-methyl-3- (difluoromethyl) -1H-pyrazole-4-carbonyl chloride and 2-bromo-4-fluoroaniline are used as starting materials and a base, the course of the process e) according to the invention can be represented by the following scheme (IV). to be illustrated:

Scheme (IV)

The pyrazolylcarboxylic acid halides of the formula (II) required as starting materials for carrying out the process e) according to the invention have already been described above in connection with the process a) according to the invention.

The fluorohalogenosilanes of the formula (VIII) furthermore required for carrying out the process e) according to the invention as starting materials have already been described above in connection with the process d) according to the invention.

The further required for carrying out the process b) according to the invention as starting materials boronic acids of the formula (V) have already been described above in connection with the method according to the invention d).

For example, use is made of N- (2-bromo-4-fluoro-phenyl) -l-methyl-3- (difluoromethyl) -1H-pyrazole-4-carboxamide and 4 ₅ 4,4 ', 4', 5,5,5 ^l , 5 '-Octamethyl-2,2'-bi-l, 3,2-dioxaborolan in the first stage and further 3-bromo-l-chlorobenzene in the second stage as starting materials, and in each stage a catalyst and a base, the Course of the process according to the invention c) are illustrated by the following scheme (V):

(Scheme V)

The halogen pyrazolecarboxanilides of the formula (TV) required as starting materials for carrying out the process c) according to the invention have already been described above in connection with the process b) according to the invention.

The diborane derivatives which are furthermore required as starting materials for carrying out the process c) according to the invention are generally defined by the formula (VI). In this formula (VI), G ³ and G ^{4 are} preferably each methyl, ethyl, propyl, butyl or together for tetramethylethylene.

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

The halobenzene derivatives which are furthermore required as starting materials for carrying out the process c) according to the invention are generally defined by the formula (VII). In this formula (VII), R ^{1 is} preferably or particularly preferably those meanings which have already been mentioned in connection with the description of the compounds of the formula (I) according to the invention as being preferred or particularly preferred for these radicals. X ³ is preferably bromine, iodine or trifluoromethylsulfonyloxy.

The halobenzene derivatives of formula (VII) are well known synthetic chemicals. Suitable diluents for carrying out the processes a) and e) according to the invention are all inert organic solvents. These include, preferably, aliphatic, alicyclic or aromatic hydrocarbons, such as, for example, petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin; halogenated hydrocarbons, such as chlorobenzene, dichlorobenzene, dichloromethane, chloroform,

Carbon tetrachloride, dichloroethane or trichloroethane; Ethers, such as diethyl ether, diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, 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 Hexarnethylphosphorsäuretriarnid.

The processes a) and e) according to the invention are optionally in the presence of a suitable

Acid acceptor / acid binder performed. As such, all customary inorganic or organic bases are suitable. These preferably include alkaline earth metal or alkali metal hydrides, hydroxides, amides, alkoxides, acetates, carbonates or bicarbonates, such as, for example, sodium hydride, sodium amide, sodium methylate, sodium ethylate, potassium tert-butoxide, sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium acetate, potassium acetate,

Calcium acetate, ammonium acetate, sodium carbonate, potassium carbonate, potassium bicarbonate, sodium bicarbonate or cesium carbonate, and tertiary amines such as trimethylamine. Triethylamine, tributylamine, N, N-dimethylaniline, N, N-dimethylbenzylamine, pyridine, N-methylpiperidine, N-methylmorpholine, N, N-dimethylammopyridine, diazabicyclooctane (DABCO) ₅ diazabicyclononene (DBN) or diazabicycloundecene (DBU).

The reaction temperatures can be varied within a relatively wide range when carrying out the processes a) and e) according to the invention. Generally carried out at temperatures of 0 ⁰ C to 150 ⁰ C, preferably at temperatures from 2O ⁰ C to 1 1O ⁰ C.

To carry out the process a) according to the invention for the preparation of the compounds of the formula (I), in general, the formula (II) is employed per mole of the pyrazolylcarboxylic acid halide

0.2 to 5 mol, preferably 0.5 to 2 mol of aniline derivative of the formula (III).

For carrying out the process e) according to the invention for preparing the compounds of the formula (IV), in general from 0.2 to 5 mol, preferably from 0.5 to 2 mol, of fluorohalogenaniline of the formula (VI.1) are employed per mole of the pyrazolylcarboxylic acid halide of the formula (II) one.

Suitable diluents for carrying out the processes b), c) and d) according to the invention are all inert organic solvents. These include preferably aliphatic, alicyclic or aromatic hydrocarbons, such as petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin; Ethers, such as diethyl ether, diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, 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 triamide; Esters, such as methyl acetate or ethyl acetate; Sulfoxides, such as dimethylsulfoxide; Sulfones, such as sulfolane; Alcohols such as methanol, ethanol, n- or i-propanol, n-, i-, s- or t-butanol, ethanediol, propane-l, 2-diol, ethoxyethanol, methoxyethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, mixtures thereof with water or pure water.

When carrying out the processes b), c) and d) according to the invention, the reaction temperatures can be varied within a substantial range. In general, one works at temperatures of 0 ⁰ C to 150 ⁰ C, preferably at temperatures of 20 ⁰ C to UO ⁰ C.

The processes b), c) according to the invention are carried out and d) if appropriate in the presence of a suitable acid acceptor. As such, all customary inorganic or organic bases are suitable. These preferably include alkaline earth metal or alkali metal hydrides, hydroxides, amides, alkoxides, acetates, fluorides, phosphates, carbonates or bicarbonates .. such as sodium hydride, sodium amide, lithium diisopropylamide, sodium methoxide, sodium ethylate, potassium tert. butoxide, sodium hydroxide, potassium hydroxide, sodium acetate, potassium acetate, sodium phosphate, potassium phosphate, potassium fluoride, cesium fluoride, sodium carbonate,

Potassium carbonate, potassium bicarbonate, sodium bicarbonate or cesium carbonate, and tertiary amines such as trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, N ₅ N-dimethylbenzylamine, pyridine, N-methylpiperidine, N-methylmorpholine, N, N-dimethylaminopyridine, diazabicyclooctane (DABCO ), Diazabicyclononene (DBN) or diazabicycloundecene (DBU).

The processes b), c) according to the invention and d) are carried out in the presence of a catalyst such as, for example, a palladium salt or complex, preferably palladium chloride, palladium acetate. Tetrakis (triphenylphosphine) palladium, bis (triphenylphosphine) - palladium dichloride or l _j l'-BisCdiphenylphosphinoJferrocenpalladiumOIJchlorid question.

Also, a palladium complex can be produced in the reaction mixture by reacting a palladium salt and a complexing ligand such as triethylphosphine. Tri-tert-butylphosphine, tricyclohexylphosphane, 2- (dicyclohexylphosphine) -biphenyl, 2- (di-tert-butyl) butylphosphine) -biphenyl, 2- (dicyclohexylphosphine) -2 '- (N, N-dimethylamino) -biphenyl,

Triphenylphosphine, tris (o-tolyl) phosphine, sodium 3- (diphenylphosphino) benzenesulfonate, tris-2- (methoxyphenyl) phosphane, 2,2'-bis (diphenylphosphine) -1,1 '-binaphthyl, 1 , 4-

Bis (diphenylphosphine) butane, 1, 2-bis (diphenylphosphane) ethane, 1,4-bis (dicyclohexylphosphane) butane, 1,2-bis (dicyclohexylphosphane) ethane, 2- (dicyclohexylphosphine) -2 ' - (N, N-dimethylamino) - biphenyl, bis (diphenylphosphino) ferrocene or tris (2,4-tert-butylphenyl) phosphite added separately to the reaction.

The concentration of the catalyst used according to the invention is from 0.01 to 10 mol%, preferably from 0.05 to 5.0 mol%, particularly preferably from 0.1 to 3.0 mol%, based on the boronic acid or diborane derivatives.

For carrying out the process b) according to the invention for the preparation of the compounds of the formula (I), in general from 1 to 15 mol, preferably from 1 to 5 mol, of boronic acid derivative of the formula (V) are employed per mole of the halopyrazolecarboxanilide of the formula (IV).

For carrying out the process c) according to the invention for the preparation of the compounds of the formula (I), in general 1 to 1 are employed per mole of the halopyrazolecarboxanilide of the formula (TV)

15 mol, preferably 1 to 5 mol of diborane derivative of the formula (VI) and 1 to 15 mol, preferably 1 to 5 mol of halobenzene derivative of the formula (VII).

For carrying out the process d) according to the invention for the preparation of the compounds of the formula (III), in general from 1 to 15 mol, preferably from 1 to 5 mol, of boronic acid derivative of the formula (V) are employed per mole of the fluorohalogenaniline of the formula (VIII).

The processes a), b), c), d) and e) according to the invention are generally carried out under atmospheric pressure. However, it is also possible under elevated or reduced pressure - generally between 0, 1 bar and 10 bar - to work.

The substances according to the invention have a strong microbicidal activity and can be used for controlling unwanted microorganisms, such as fungi and bacteria, in crop protection and in the protection of materials.

Fungicides can be used for the control of Plasmodiophoromycetes, Oomycetes, Chytriomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes. Bactericides can be used in crop protection for controlling Pseudomonadaceae, Rhizobiaceae, Enterobacteriaceae, Corynebacteriaceae and Streptomycetaceae.

By way of example but not limitation, some pathogens of fungal and bacterial diseases, which fall under the above-enumerated generic terms, are named:

5 Xanthomonas species, such as Xanthomonas campestris pv. Oryzae;

Pseudomonas species, such as Pseudomonas syringae pv. Lachryrnans;

Erwinia species, such as Erwinia amylovora;

Pythium species such as Pythium ultimum;

Phytophthora species, such as Phytophthora infestans;

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

Pseudoperonospora cubensis;

Plasmopara species, such as Plasmopara viticola;

Bremia species, such as Bremia lactucae;

Peronospora species such as Peronospora pisi or P. brassicae;

l s Erysiphe species, such as Erysiphe graminis;

Sphaerotheca species, such as Sphaerotheca fuliginea;

Podosphaera species, such as Podosphaera leucotricha;

Venturia species, such as Venturia inaequalis;

Pyrenophora species, such as, for example, Pyrenophora teres or P. graminea

2ö (conidia form: Drechslera, Syn: Helminthosporium);

Cochliobolus species, such as Cochliobolus sativus

(Conidia form: Drechslera, Syn: Helminthosporium); Uromyces species, such as Uromyces appendiculatus;

Puccinia species, such as Puccinia recondita;

Sclerotinia species, such as Sclerotinia sclerotiorum;

Tilletia species, such as Tilletia caries;

Ustilago species such as Ustilago nuda or Ustilago avenae;

Pellicularia species. such as Pellicularia sasakii;

Pyricularia species, such as Pyricularia oryzae;

Fusarium species such as Fusarium culmorum;

Botrytis species, such as Botrytis cinerea;

Septoria species such as Septoria nodorum;

Leptosphaeria species, such as Leptosphaeria nodorum;

Cercospora species, such as Cercospora canescens;

Altemaria species, such as Alternaria brassicae;

Pseudocercosporella species, such as Pseudocercosporella herpotrichoides.

The active compounds according to the invention also have a strong tonic effect in plants. They are therefore suitable for mobilizing plant-own defenses against attack by unwanted microorganisms.

In the present context, plant-enhancing (resistance-inducing) substances are to be understood as meaning substances which are capable of stimulating the defense system of plants in such a way that the treated plants largely go on to be subsequently inoculated with undesired microorganisms

Develop resistance to these microorganisms.

Undesirable microorganisms in the present case are phytopathogenic fungi, bacteria and viruses. The substances according to the invention can therefore be used to plants within a certain period of time after the treatment against the infestation by said pathogens protect. The period of time within which protection is afforded generally extends from 1 to 10 days, preferably 1 to 7 days after the treatment of the plants with the active ingredients.

The good plant tolerance of the active ingredients in the necessary concentrations for controlling plant diseases allows treatment of aboveground plant parts, of plant and seed, and the soil.

The active compounds according to the invention are also suitable for increasing crop yield. They are also low toxicity and have good plant tolerance.

The active compounds according to the invention may optionally also be used in certain concentrations and application rates as herbicides, for influencing plant growth and for controlling animal pests. If necessary, they can also be used as intermediate and

Use precursors for the synthesis of other active ingredients.

Erfϊndungsgemäß all plants and parts of plants can be treated. In this context, plants are understood as meaning all plants and plant populations, such as desired and undesired wild plants or crop plants (including naturally occurring crop plants). Crop plants can be plants produced by conventional breeding and

Optimization methods or by biotechnological and genetic engineering methods or combinations of these methods can be obtained, including the transgenic plants and including protected by plant breeders' rights or non-protectable plant varieties. Plant parts are to be understood as meaning all aboveground and underground parts and organs of the plants, such as shoot, leaf, flower and root, examples being leaves, needles, stems,

Strains, flowers, fruiting bodies, fruits and seeds, as well as roots, tubers and rhizomes. The plant parts also include crops and vegetative and generative propagation material, such as cuttings, tubers, rhizomes, offshoots and seeds.

The treatment according to the invention of the plants and plant parts with the active substances takes place directly or by acting on their surroundings. Habitat or storage room after the usual

Treatment methods, e.g. by dipping, spraying, vaporizing, atomizing, spreading, spreading and in propagation material, in particular in seeds, further by single or multi-layer wrapping.

In the protection of materials, the substances according to the invention can be used to protect industrial materials against infestation and destruction by undesired microorganisms. Technical materials as used herein mean non-living materials that have been prepared for use in the art. For example, technical materials to be protected from microbial alteration or destruction by the active compounds of the present invention may be adhesives, glues, paper and cardboard, textiles, leather, wood, paints and plastics, coolants and other materials infested or decomposed by microorganisms can. In the context of the materials to be protected are also parts of production plants, such as cooling water circuits, called, which can be affected by the proliferation of microorganisms. In the context of the present invention are as technical materials preferably adhesives, glues, papers and cardboard, leather, wood, AnstrichmitteL cooling lubricant lo and heat transfer fluids, more preferably wood.

As microorganisms that can cause degradation or a change in the technical materials, for example, bacteria, fungi, yeasts, algae and mucus organisms may be mentioned. The active compounds according to the invention preferably act against fungi, in particular molds, wood-discolouring and wood-destroying fungi (Basidiomycetes) and against slime organisms and algae.

15 For example, microorganisms of the following genera are mentioned:

Alternaria, such as Alternaria tenuis,

Aspergillus, such as Aspergillus niger,

Chaetomium. like Chaetomium globosum,

Coniophora, like Coniophora puetana,

20 Lentinus, like Lentinus tigrinus,

Penicillium, such as Penicillium glaucum,

Polyporus, such as Polyporus versicolor,

Aureobasidium, such as Aureobasidium pullulans,

Sclerophoma, such as Sclerophoma pityophila,

25 Trichoderma, like Trichoderma viride,

Escherichia, like Escherichia coli, Pseudomonas, such as Pseudomonas aeruginosa,

Staphylococcus, such as Staphylococcus aureus.

In addition, can be reduced by the treatment according to the invention, the mycotoxin content in the crop and the food and feed produced therefrom. Particularly, but not exclusively, the following mycotoxins may be mentioned here: deoxynivalenol (DON), nivalenol, 15-ac-DON, 3-acyl

DON, T2 and HT2 toxin, fumonisins, zearalenone, moniüformin, fusarin, diaceotoxyscirpenol (DAS), beauvericin, enniatine, fusaroproliferin, fusarenol, ochratoxins, patulin, ergot alkaloids and aflatoxins, which may be caused, for example, by the following fungi: Fusarium speα such as Fusarium acuminatum, F. avenaceum, F. crookwellense, F. culmorum, F. graminearum (Gibberella zeae), io F. equiseti, F. fujikoroi, F. musarum, F. oxysporum, F. proliferatum, F. poae, F. pseudograminearum, F. sambucinum, F. scirpi, F. semitectum, F. solani, F. sporotrichoides, F. langsethiae, F. subglutinans, F. tricinctum, F. verticillioides, and others as well as of Aspergillus speα, Penicillium spec., Claviceps purpurea, Stachybotrys spec. et al

Depending on their respective physical and / or chemical properties, the active compounds can be converted into the customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, ultrapure encapsulations in polymeric substances and in seed coating compositions, and ULV caustic and warm mist formulations.

These formulations are prepared in a known manner, e.g. by mixing the active compounds with extenders, ie liquid solvents, liquefied gases under pressure and / or solid

20 carriers, if appropriate using surface-active agents, ie emulsifiers and / or dispersants and / or foam-forming agents. In the case of using water as an extender, e.g. also organic solvents can be used as auxiliary solvents. Suitable liquid solvents are essentially: aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, e.g. Petroleum fractions, alcohols, such as butanol or glycol, and 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, and water. By liquefied gaseous diluents or carriers are meant those liquids which are gaseous at normal temperature and under normal pressure, e.g. Aerosol propellants, such as halogenated hydrocarbons as well as butane, propane, nitrogen and

Carbon dioxide. Suitable solid carriers are: for example ground natural minerals, such as kaolins, Clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals such as fumed silica, alumina and silicates. Suitable solid carriers for granules are: eg broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules of inorganic and organic flours and granules of organic material such as sawdust, coconut shells, corn cobs and tobacco stalks. When

Emulsifying and / or foaming agents are suitable: e.g. nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. Alkylarylpolyglycol ethers, alkylsulfonates, alkylsulfates, arylsulfonates and protein hydrolysates. Suitable dispersants are: e.g. Lignin-sulphite liquors and methylcellulose.

Adhesives such as carboxymethylcellulose, natural and synthetic powdery, granular or latex-like polymers can be used in the formulations, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, as well as natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids. Other additives may be mineral and vegetable oils.

Dyes such as inorganic pigments, e.g. Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as

Salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used.

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

The active compounds according to the invention can be used as such or in their formulations also in admixture with known fungicides, bactericides, acaricides, nematicides or insecticides, so as to prevent, for example, the spectrum of action or to prevent the development of resistance. In many cases, synergistic effects are obtained, ie the effectiveness of the mixture is greater than the effectiveness of the individual components. For example, the following compounds may be used as mixing partners:

fungicides:

1. Inhibition of nucleic acid synthesis

Benalaxyl, benalaxyl-M, bupirimate, chiralaxyl, clozylacon, dimethirimol, ethirimol, furalaxyl, 5-hymexazole, mefenoxam, metalaxyl, metalaxyl-M, ofurace, oxadixyl, oxolinic acid.

2. Inhibition of mitosis and cell division

Benomyl, carbendazim, diethofencarb, fuberidazole, pencycuron, thiabendazole, thiophanate-methyl, zoxamide.

3. Inhibition of the respiratory chain o 3.1 complex I

diflumetorim

3.2 Complex II

Boscalid, Carboxin, Fenflxram, Flutolanil. Furametpyr, furmecyclox, mepronil, oxycarbine, penthiopyrad, thifluzamide. 5 3.3 Complex III

Amisulbrom, Azoxystrobin, Cyazofamide, Dimoxystrobin, Enestrobin, Famoxadone, Fenamidon, Fluoxastrobin, Kresoximethyl, Metominostrobin, Orysastrobin, Picoxystrobin, Pyraclostrobin, Trifloxystrobin.

3.4 decouplers o dinocap, fluazinam, methyldinocap.

3.5 Inhibition of A TP production

Fentin acetate, fentin chloride, fentin hydroxide, silthiofam. 4. Inhibition of amino acid and protein biosynthesis

Andoprim, blasticidin-S, cyprodinil, kasugamycin, kasugamycin hydrochloride hydrate, mepanipyrim, pyrimethanil.

5. Inhibition of signal transduction

Fenpiclonil, fludioxonil, quinoxyfen.

6. Inhibition of fat and membrane synthesis

Chlozolinate, iprodione, procymidone, vinclozolin, pyrazophos, edifenphos, iprophf (IBP), isoprothiolane, tolclofos-methyl, biphenyl, iodocarb, propamocarb, propamocarbohydrochloride.

7. Inhibition of ergosterol biosynthesis

Fenhexamid, azaconazole, bitertanol, bromuconazole, cyproconazole, diclobutrazole, difenoconazole, diniconazole, diniconazole-M, epoxiconazole, etaconazole, fenbuconazole, fluquinconazole, flurprimidol, flusilazole, flutriafol, furconazole, furconazole-cis, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, Paclobutrazole, penconazole, propiconazole, prothioconazole, pyrifenox, simeconazole, tebuconazole,

Tetraconazole, Triadimefon, Triadimenol, Triticonazole, Uniconazole, Voriconazole, Imazalil, Imazalilsulfat, Oxpoconazol, Fenarimol, Fluφrimidol, Nuarimol, Pyrifenox, Triforin, Pefurazoate, Prochloraz, Triflurnizol, Triforin, Viniconazol, Aldimoφh, Dodemoφh, Dodemoφhacetat, Fenpropidin, Fenpropimoφh, Tridemoφh, Spiroxamine, naftifine, pyributicarb, terbinafine.

8. Inhibition of cell wall synthesis

Benthiavalicarb, Dimethomoφh, Flumoφh, Iprovalicarb, Polyoxins, Polyoxorim, Validamycin

A.

9. Inhibition of melanin biosynthesis

Capropamide, diclocymet, fenoxanil, phtalid, pyroquilone, tricyclazole.

10. resistance induction

Acibenzolar-S-methyl, probenazole, tiadinil. 11. Multisite

Bordeaux mixture, captafol, captan, chlorothalonil, copper salts such as: copper hydroxide, copper naphthenate, copper oxychloride, copper oxide, copper sulfate, oxine-copper and, dichlofluanid, dithianon, dodin, dodine free base, ferbam, fluorofolpet, folpet, guazatine, guazatin acetate, iminoctadine, iminoctadinalbesilat , Iminoctadine triacetate, maricopter. mancozeb,

Maneb, metiram, metiram zinc, propineb, sulfur and sulfur preparations containing calcium polysulphide, thiram, tolylfluanid, zineb, ziram.

12. Unknown Mechanisms of Action

Amibromdole, benthiazole, bethoxazine, capsimycin, carvone, quinomethionate, chloropicrin, cufraneb, cyflufenamid, cymoxanil, dazomet, debacarb, dichlorophen, diclomezine, dicloran,

Difenzoquat, Difenzoquat Methylsulphate, Diphenylamine, Ferimzone, Flumetover. Fluopicolide, fluoroimide, flusulfamide, fosetyl-aluminum, fosetyl-calcium, fosetyl-sodium, hexachlorobenzene. 8-hydroxyquinoline sulfate, irumamycin, methasulphocarb, methyl isothiocyanate, metrafenone, mildiomycin, natamycin, nickel dimethyldithiocarbamate, nitrothal isopropyl, octhilinone, oxamocarb, oxyfenthiine, pentachlorophenol and salts, 2-phenylphenol and salts, phosphorous acid and salts, piperaline, propamocarb fosetylate, Propanosine - sodium. Proquinazide, Pyrrolnitrin, Quintozen, Tecloftalam, Tecnazene, triazoxide, trichlamide, zarilamide and 2-amino-4-methyl-N-phenyl-5-thiazolecarboxamide, 2-chloro-N- (2,3-dihydro-l, l, 3 trimethyl-1H-inden-4-yl) -3-pyridinecarboxamide, 3- [5- (4-chlorophenyl) -2,3-dimethylisoxazolidin-3-yl] pyridine, cis-1- (4-chlorophenyl) -2- ( lH-l, 2,4-triazol-1-yl) -cycloheptanol, 2,4-dihydro-5-methoxy-2-methyl-4 - [[[[l- [3- (trifluoromethyl) -phenyl] -ethyl ] -amino] -oxy] -methyl] -phenyl] - 3H-l, 2,3-triazol-3-one, methyl 1- (2,3-dihydro-2,2-dimethyl-1H-indene-1) yl) -1H-imidazole-5-carboxylate, methyl 2 - [[[cyclopropyl [(4-methoxyphenyl) imino] methyl] thio] methyl] phenyl} -3-methoxyacrylate. , Methyl 3 - (4-chloro-phenyl) -3 - {[N- (isopropoxycarbonyl) -valyl] -amino} -propanoate, 4-Chloro-alpha-propynyloxy-N- [2- [3-methoxy-4- (2-propynyloxy) phenyl] ethylJ-benzacetamide, 2- (2-

{[6- (3-Chloro-2-methylphenoxy) -5-fluoro-pyrimidin-4-yl] oxy} -phenyl) -2- (methoxy-amino) -N-methylacetamide, (2S) -N- [2- [4-] [3- (4-chlorophenyl) -2-propynyl] oxy] -3-methoxyphenyl] ethyl] -3-methyl-2 - [(methylsulfonyl) amino] butanamide, 5-chloro-7- (4-methylpiperidine-1 -yl) -6- (2,4,6-trifluorophenyl) [l, 2,4] triazolo [l, 5-a] pyrimidiryl, 5-chloro-6- (2,4,6-trifluorophenyl) -Nr ( 1R) - 1, 2,2-trimethylpropyl] [1,2,4] triazolo [1,5-a] pyrimidin-7-amine, 5-chloro-N - [(1R) -1,2-dimethylpropyl ] -6-

(2,4,6-trifluorophenyl) [l, 2,4] triazolo [l, 5-a] pyrimidin-7-amine, N- [1- (5-bromo-3-chloropyidin-2-yl) ethyl] -2 , 4-Dichloronicotinamide, N- (5-bromo-3-chloropyridin-2-yl) methyl-2,4-dichloronotinotinamide, N- [1- (5-Bromo-3-chloropyridin-2-yl) ethyl] -2-fluoro-4-iodo-nicotinamide, 2-butoxy-6-iodo-3-propyl-benzopyranon-4-one, N - [2- (4 - {[3- (4-Chloro-phenyl) -prop-2-yn-1-yl] oxy} -3-methoxyphenyl) -ethyl] -N-2- (methylsulfonyl) -valinamide, N - {(2 ) - [(Cyclopropylmethoxy) imino] [6- (difluoromethoxy) -2,3-difluorophenyl] methyl} -2-phenylacetamide, N- (4-chloro-2-nitrophenyl) -N-ethyl-4-methylbenz 5 sulfonamide, N- (3-ethyl-3,5,5-trimethylcyclohexyl) -3-formylanino-2-hydroxybenzamide, 2 - [[[[l-

[3 (1-Fluoro-2-phenylethyl) oxy] phenyl] ethylidene] amino] oxy] methyl] -alpha (methoxyimino) -N-methyl-alpha-E-benzoacetamide, N- {2- [3-chloro-5- (trifluoromethyl ) pyridin-2-yl] ethyl} -2-

(trifluoromethyl) benzamide, N- (3 ', 4'-dichloro-5-fluorobi-phenyl-2-yl) -3- (difluoromethyl) -1-methyl-1H-pyrazole-4-carboxamide, N- (6-methoxy 3-pyridinyl) cyclopropane carboxamide, 1- [(4-methoxy-1-phenoxy) methyl] -2,2-dimethylpropyl-1H-imidazole-1-carboxylic acid, O- [1 - [(4-methoxyphenoxy) - methyl] -2,2-dimethylpropyl] -1H-imidazole-1-carbothioic acid, 2,3,5,6-tetrachloro-4- (methylsulfonyl) -p} τidine, 3,4,5-trichloro 2,6-pyridinedicarbonitrile.

bactericides:

Bronopol, dichlorophen, nitrapyrin, nickel dimethyldithiocarbamate, kasugamycin, octhilinone, furan I _5-carboxylic acid, oxytetracycline, probenazole, streptomycin, tecloftalam, copper sulphate and other copper

Preparations.

Insecticides / acaricides / nematicides:

1. Acetylcholinesterase (AChE) inhibitors

/ 1 carbamate

20 alanycarb, aldicarb, aldoxycarb, allyxycarb, aminocarb, azamethiphos, bendiocarb,

Benfuracarb, bufencarb, butacarb, butocarboxim, butoxycarboxim, carbaryl, carboofuran, carbosulfan, chloethocarb, coumaphos, cyanofenphos, cyanophos, dimetilane, ethiofencarb, fenobucarb, fenothiocarb, formetanate, furathiocarb, isoprocarb, metam-sodium, methiocarb, methomyl, metolcarb, Oxamyl, pirimicarb, promecarb,

25 Propoxur, Thiodicarb, Thiofanox, Triazamate, Trimethacarb, XMC, Xylylcarb.

1.2 Organophosphates

Acephate, Azamethiphos, Azinphos (-methyl, -ethyl), Bromophos-ethyl, Bromfenvinfos (-methyl), Butathiofos, Cadusafos, Carbophenothion, Chloroethoxyfos, Chlorfenvinphos, Chlormephos, Chloφyrifos (-methylAethyl), Coumaphos, Cyanofenphos, Cyanophos, Chlorfenvinphos, demeton-S-methyl, demeton-S-methylsulphon, dialifos, diazinon, dichlofenthione, dichlorvos / DDVP, dicrotophos, dimethoates, dimethylvinphos, dioxabenzofos, disulphoton, EPN, ethion, ethoprophos, etrimfos, famphur, fenamiphos, fenitrothion, Fensulfothion, Fenthion, Flupyrazofos, Fonofos, Formothion,

5 Fosmethilane, Fosthiazate, Heptenophos, Iodofenphos, Iprobenfos, Isazofos, Isofenphos,

Isopropyl O-Salicylate, Isoxathione, Malathion, Mecarbam, Methacrifos, Methamidophos, Methidathione, Mevinphos, Monocrotophos, Naled, Omethoate, Oxydemeton-methyl, Parathion (-methyl / -ethyl), Phenthoate, Phorate, Phosalone, Phosmet, Phosphamidone, Phosphocarb, Phoxim, pirimiphos (-methylethyl), profenofos, propaphos, o propetamphos, prothiofos, prothoates, pyraclofos, pyridaphenthione, pyridathion,

Quinalphos, Sebufos, Sulfotep, Sulprofos, Tebupirimfos, Temephos, Terbufos, Tetrachlorvinphos, Thiometon, Triazophos, Triclorfon, Vamidothion.

2. Sodium Channel Modulators / Voltage-Dependent Sodium Channel Blockers

2.1 Pyrethroids 5 acrinathrin, allethrin (d-cis-trans, d-trans), beta-cyfluthrin, bifenthrin, bioallethrin,

Bioallethrin S-cyclopentylisomer, bioethanomethrin, biopermethrin, bioresmethrin, chlovaporthrin, cis-cypermethrin, cis-resmethrin, cis-permethrin, clocytlirine, cycloprothrin, cyfluthrin, cyhalothrin, cypermethrin (alpha-, beta-, theta-, zeta-) , Cyphenothrin, DDT, deltamethrin, empenthrin (lR-isomer), esfenvalerate, etofenprox, δfenfluthrin, fenpropathrin, fenpyrithrine, fenvalerate, flubrocythrinates, flucythrinates,

Flufenprox, Flumethrin, Fluvalinate, Fubfenprox, Gamma-Cyhalothrin, Imiprothrin, Kadethrin, Lambda-Cyhalothrin, Metofluthrin, Permethrin (cis, trans), Phenothrin (IR trans isomer), Prallethrin, Profuthrin, Protrifenbute, Pyresmethrin, Resmethrin, RU 15525, Silafluofen, Tau Fluvalinate, Tefluthrin, Terallethrin, Tetramethrin (IR isomer), 5 Tralomethrin, Transfluthrin, ZXI 8901, Pyrethrin (pyrethrum).

2.2 Oxadiazines

eg indoxacarb. 3. Acetylcholine receptor agonists / antagonists

3.1 chloronicotinyls / neonicotinoids

Acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram, nithiazines, thiacloprid, thiamethoxam.

3.2 nicotine

Bensultap, Cartap.

4. Acetylcholine receptor modulators

4.1 Spinosyns

e.g. Spinosad.

5. GABA-driven chloride channel antagonists

5.1 Cyclodienes Organochlorines

Camphechlor, chlordane, endosulfan, gamma-HCH, HCH, heptachlor, lindane, methoxychlor.

5.2 Fiproles

Acetoprole, ethiprole, fipronil, vaniliprole.

6. Chloride Channel Activators

6.1 Mectins

Abamectin, avermectin, emamectin, emamectin benzoate, ivnectin, milbemectin, milbemycin.

7. Juvenile hormone mimetics

Diofenolan, Epofenonane, Fenoxycarb, Hydroprene, Kinoprene, Methoprene, Pyriproxifen, Triprene. 8. ecdysonagonists / disruptors

8.1 Diacylhydrazines

Chromafenozide, Halofenozide, Methoxyfenozide, Tebufenozide.

9. Inhibitors of chitin biosynthesis

9.1 Benzoylureas

Bistrifluron, chlorofluazuron, diflubenzuron, fluazuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, penfluron, teflubenzuron, trifluoron)

9.2 Buprofezin

9.3 Cyromazine

10. Inhibitors of oxidative phosphorylation, ATP disruptors

10.1 Diafenthiuron

10.2 Organotin

Azocyclotin, cyhexatin, fenbutatin oxides.

11. Decoupling of the oxidative phosphorylation by interruption of the H-

Proton

/./ Pyrroles

e.g. Chlorfenapyr.

11.2 Dinitrophenols

Binapacyrl, dinobutone, dinocap, DNOC. 12. Site I electron transport inhibitors

12.1 METI's

Fenazaquin, Fenpyroximate, Pyrimidifen, Pyridaben, Tebufenpyrad, Tolfenpjtad.

12.2 Hydramethylnone

12.3 Dicofol

13. Site H Electron Transport Inhibitors

13.1 Rotenone

14. Site III Electron Transport Inhibitors

14.1 Acequinocyl, Fluacrypyrim

15. Microbial disruptors of insect intestinal membrane

Bacillus thuringiensis strains

16. Inhibitors of fat synthesis

16.1 Tetronic acids

e.g. Spirodiclofen, spiromesifen. 16.2 Tetramic acids

e.g. 3- (2,5-Dimethylphenyl) -8-methoxy-2-oxo-1-azaspiro [4.5] dec-3 -en-4-yl ethyl carbonate (also known as: Carbonic acid, 3- (2,5-dimethylphenyl) -8-methoxy-2-oxo-1-azaspiro [4.5] dec-3-en-4-yl ethyl ester, CAS Reg. No .: 382608-10-8) and carbonic acid, cis-3 ( 2,5-dimethylphenyl) -8-methoxy-2-oxo-1-azaspiro [4.5] dec-3-en-4-yl ethyl ester (CAS Reg. No .: 203313-25-1).

17. Carboxamides

eg flonicamide 18. Octopaminergic agonists

e.g. amitraz

19. Inhibitors of magnesium-stimulated ATPase

e.g. propargite

20. phthalamides

e.g. N 2 - [l, l -dimethyl-2- (methylsulfonyl) ethyl] -3-iodo-N - [2-methyl-4- [l, 2,2,2-tetrafluoro-1- (trifluoromethyl) ethyl] phenyl] -l, 2-benzenedicarboxamide (CAS Reg. No .: 272451-65-7), flubendiamide.

21. Nereistoxin analogs

e.g. Thiocyclam hydrogen oxalate, thiosultap sodivun.

22. Biologics, hormones or pheromones

e.g. Azadirachtin, Bacillus spec., Beauveria spec., Codlemone, Metarrhicon spec., Paecilomyces spec., Thuringiensin, Verticillium spec.

23. Active substances with unknown or non-specific mechanisms of action

23.1 Fumigant

e.g. Aluminum phosphides, methyl bromides, sulfuryl fluorides.

23.2 Selective feed inhibitors

e.g. Cryolites, flonicamid, pymetrozines.

23.3 mite growth inhibitors

e.g. Clofentezine, etoxazole, hexythiazox.

23.4 Other

Amidoflumet, Benclothiaz, Benzoximate, Bifenazate, Bromopropylate, Buprofezin, Chinomethionate, Chlordimeform, Chlorobenzilate, Chloropicrin, Clothiazoben, Cyclo- Prene, Cyflumetofen, Dicyclanil, Fenoxacrim, Fentrifanil, Flubenzimine, Flufenerim, Flutenzin, Gossyplure, Hydramethylnone, Japonilure, Metoxadiazone, Petroleum, Piperonyl butoxide, Potassium oleate, Pyrafluprole, Pyridalyl, Pyriprole, Sulfluramid, Tetradifon, Tetrasul, Triarathene, Verbutin,

furthermore, the compound 3-methyl-phenyl-propylcarbamate (Tsumacide Z), the compound 3- (5-chloro-3-pyridinyl) -8- (2,2,2-trifluoroethyl) -8-azabicyclo [3.2.1] octane 3-carbonitrile (CAS Reg. No. 185982-80-3) and the corresponding 3-endo isomer (CAS Reg. No. 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 known active substances, such as herbicides or with fertilizers and growth regulators is possible.

In addition, the compounds of the formula (I) according to the invention also have very good antifungal effects. They have a very broad antimycotic spectrum of action, in particular against dermatophytes and yeasts, mold and diphasic fungi (for example against Candida species such as Candida albicans, Candida glabrata) as well as Epidermophyton floccosum, Aspergillus species such as Aspergillus niger and Aspergillus fumigatus, Trichophyton species such as

Trichophyton mentagrophytes, Microsporon species such as Microsporon canis and audouinii. The list of these fungi is by no means a limitation of the detectable mycotic spectrum, but has only an explanatory character.

The active compounds can be used as such, in the form of their formulations or the use forms prepared therefrom, such as ready-to-use solutions, suspensions, wettable powders, pastes, soluble powders,

Dust and granules are applied. The application is done in the usual way, e.g. by pouring, spraying, spraying, scattering, dusting, foaming, brushing, etc. It is also possible to apply the active ingredients by the ultra-low-volume method or to inject the active ingredient preparation or the active ingredient itself into the soil. It can also be the seed of the plants to be treated.

When using the active compounds according to the invention as fungicides, the application rates can be varied within a relatively wide range, depending on the mode of administration. In the treatment of parts of plants, the application rates of active ingredient are generally between 0.1 and 10,000 g / ha, preferably between 10 and 1,000 g / ha. In the seed treatment, the application rates of active ingredient are generally between 0.001 and 50 g per kilogram of seed, preferably between 0.01 and 10 g per Kilograms of seed. In the treatment of the soil, the application rates of active ingredient are generally between 0.1 and 10,000 g / ha, preferably between 1 and 5,000 g / ha.

As already mentioned above, according to the invention all plants and their parts can be treated.

In a preferred embodiment, wild-type or by conventional biological breeding methods, such as crossing or protoplast fusion obtained plant species and

Treated plant varieties and their parts. In a further preferred embodiment, transgenic plants and plant cultivars which may be obtained by genetic engineering methods in

Combination with conventional methods would be treated (Genetically Modified Organisms) and their parts treated. The term "parts" or "parts of plants" or "plant parts" has been explained above.

It is particularly preferred according to the invention to treat plants of the respective commercially available or in use plant cultivars. Plant varieties are understood as meaning plants having new traits which have been bred by conventional breeding, by mutagenesis or by recombinant DNA techniques. These may be varieties, breeds, biotypes and genotypes.

Depending on the plant species or plant cultivars, their location and growth conditions (soils, climate, vegetation period, diet), the treatment according to the invention may also give rise to superadditive ("synergistic") effects. Thus, for example, reduced application rates and / or extensions of the spectrum of action and / or an increase in the effect of the substances and agents usable in the invention, better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to water or soil salt content, increased flowering power facilitated harvest, acceleration of ripeness, higher crop yields, higher quality and / or higher nutritional value of the harvested products, higher shelf life and / or machinability of the harvested products, which exceed the actual expected effects.

The preferred plants or plant varieties to be treated according to the invention to be treated include all plants which, as a result of the genetic engineering modification, obtained genetic material which gives these plants particularly advantageous valuable properties ("traits"). Examples of such properties are better plant growth, increased tolerance to high or low temperatures, increased

Tolerance to dryness or to water or soil salt content, increased flowering power, facilitated harvest, acceleration of ripeness, higher crop yields, higher quality and / or higher nutritional value of the harvested products, higher shelf life and / or machinability of the harvested products. Further and particularly emphasized examples of such properties are an increased defense of the plants against animal and microbial pests, as against insects, mites, phytopathogenic fungi, bacteria and / or viruses as well as an increased tolerance of the plants to certain herbicidal active substances. Examples of transgenic plants include the important crops such as cereals (wheat, rice), corn, soy, potato, cotton, rapeseed and fruit plants (with the fruits apples, pears, citrus fruits and grapes), with corn, soy, potato, cotton and rapeseed should be highlighted. Traits which are particularly emphasized are the increased defense of the plants against insects by toxins which are formed in the plants, in particular those which are produced by the genetic material from Bacillus thuringiensis (for example by the genes CryΙA (a), CryΙA (b), CryΙA (c), CryllA, CrylllA, CryIIIB2, Cry9c Cry2Ab, Cry3Bb and CrylF and combinations thereof) are produced in the plants (hereinafter "Bt plants"). As properties ("traits") are also particularly emphasized the increased defense of plants against fungi, bacteria and viruses

Systemic acquired resistance (SAR), systemin, phytoalexins, elicitors and resistance genes and correspondingly expressed proteins and toxins. Traits which are furthermore particularly emphasized are the increased tolerance of the plants to certain herbicidally active compounds, for example imidazolinones, sulfonylureas, glyphosate or phosphinotricin (eg "PAT" gene). The genes which confer the desired properties ("traits") can also occur in combinations with one another in the transgenic plants. Examples of "Bt plants" are maize varieties, cotton varieties, soya bean varieties and potato varieties which are sold under the trade names YIELD GARD ^® (for example maize, cotton, soya beans), KnockOut ^® (for example maize), StarLink ^® (for example maize), Bollgard ^® ( cotton), Nucoton ^® (cotton) and NewLeaf ^® (potato) veit rubbed. Examples of herbicide-tolerant plants are maize varieties, cotton varieties and soybean varieties which are resistant under the trade names Roundup Ready ^® (tolerance to glyphosate, for example maize, cotton, soya bean), Liberty Link ^® (tolerance to phosphinotricin, for example oilseed rape), IMI ^® (tolerance Imidazolinone) and STS ^® (tolerance to sulfonylureas such as corn) are sold. Herbicide-resistant (conventionally grown on herbicide tolerance) plants are also the varieties marketed under the name Clearfield ^® (eg corn) mentioned.

Of course, these statements also apply to future or future marketed plant varieties with these or future developed genetic traits. The plants listed can be treated particularly advantageously according to the invention with the compounds of the general formula (I) or the Wirkstoffinischungen invention. The preferred ranges given above for the active compounds or mixtures also apply to the treatment of these plants. Particularly emphasized is the plant treatment with the compounds or mixtures specifically mentioned in the present text.

Preparation Examples

Example 1: N- (2-bromo-4-fluorophenyl) -3- (difluoromethyl) -1-methyl-1H-pyrazole-4-carboxamide

To a solution consisting of 2.16 g (11.4 mmol) of 2-bromo-4-fluoroaniline in 10 ml of acetonitrile, 3.14 g (22.7 mmol) of potassium carbonate are added. Subsequently, a solution consisting of 2.4 g (12.5 mmol) of 1-methyl-3- (trifluoromethyl) -1H-pyrazole-4-carbonyl chloride in 4 ml of acetonitrile is added dropwise and the reaction mixture stirred for 16 hours at 50 ° C. For workup, the reaction mixture is cooled to room temperature, filtered, concentrated and the resulting solid recrystallized from diisopropyl ether. This gives 2.1 g of N- (2-bromo-4-fluorophenyl) -3- (difluoromethyl) -1-methyl-1H-pyrazole-4-carboxamide (53% of theory, logP acid 2.26).

Example 2 Preparation of N- (4'-chloro-5-fluorobiphenyl-2-yl) -3- (difluoro-ethyl) -1-methyl-1H-pyrazole-4-carboxamide (variant (b))

Under an inert gas atmosphere, 16 mg (2 mol%) of tetrakis (triphenylphosphine) palladium (0) are added to a suspension consisting of 0.244 g (0.7 mmol) of N- (2-bromo-4-fluorophenyl) -3- (difluoromethyl) -1-methyl -LH-pyrazole-4-carboxamide, and 120 mg (0.8 mmol) of 4-chlorophenylboronic acid in 8 ml of toluene, 1.5 ml of ethanol and 5 ml of 4 M Na ₂ CO 3 sols. The reaction mixture is stirred for 8 hours at 80 ^° C. For workup, the phases are separated and the organic phase is filtered and concentrated in vacuo. Column chromatography (gradient cyclohexane / ethyl acetate) provides 134 mg of N- (4'-chloro-5-fluorobiphenyl-2-yl) -3- (difluoromethyl) -1-methyl-1H-pyrazole-4-carboxamide (50% of theory, logP acid 3.02).

Example 3 Preparation of N- (4'-chloro-5-fluorobiphenyl-2-yl) -3- (difluoro-methyl) -1-methyl-1H-pyrazole-4-carboxamide (variant (a))

To a solution consisting of 771 mg (3.2 mmol) of 4'-chloro-5-fluorobiphenyl-2-amine and 1.5 ml (10.9 mmol) of triethylamine in 9 ml of dichloromethane 850 mg (4.4 mmol) of l-methyl-3- (difluoromethyl ) -LH-pyrazole-4-carbonyl chloride in 7 ml of dichloromethane. The reaction mixture is stirred for 56 hours at room temperature and then treated with 15 ml of water. The phases are separated and the aqueous phase is washed three times with 20 ml each time

Extracted vinegar. The combined organics are dried over magnesium sulfate, filtered and concentrated in vacuo. Column chromatography (gradient n-heptane / ethyl acetate) gives 867 mg of N- (4'-chloro-5-fluorobiphenyl-2-yl) -3- (difluoromethyl) -1) -1-methyl-1H-pyrazole-4-carboxamide (cf. 60% of theory, logP sour 3.01).

Claims

claims

1. 3-difluoromethylpyrazolylcarboxanilides of the formula (I)

in which

R ¹ represents halogen, cyano, nitro, C _r C ₆ alkyl, C ₂ -C ₆ alkenyl, Ci-C ₄ alkoxy, QC ₄ - alkylthio, Ci-C ₄ alkylsulfonyl, C ₃ -C ₆ cycloalkyl or ₄ haloalkyl, Cr C ₄ haloalkoxy, _{Ci-C4-haloalkylthio} or C ₄ haloalkylsulfonyl stands for dC, each having 1 to 5 halogen atoms.

3-Difluoromethyl-pyrazolylcarboxanilides according to claim 1, wherein the radical R ^{1 is} selected from the group consisting of fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, methylthio, ethylthio, n- or i-propylthio, cyclopropyl, trifluoromethyl, trichloromethyl, trifluoroethyl, difluoromethoxy, trifluoromethoxy, difluorochloromethoxy, trifluoroethoxy, difluoromethylthio, difluorochloromethylthio or trifluoromethylthio.

3-Difluoromethyl-pyrazolylcarboxanilides according to claim 1 or 2, wherein the radical R ^{1 is} a halogen atom.

3-Difluoromethyl-pyrazolylcarboxanilides according to any one of claims 1 to 3, wherein the radical R ^{1 is} chlorine.

3-Difluoromethyl-pyrazolylcarboxanilide according to one of Claims 1 to 4, of the formula (Ia)

3-Difluoromethyl-pyrazolylcarboxanilide according to one of Claims 1 to 5, of the formula (Ib)

7. A process for preparing 3-difluoromethyl-pyrazolylcarboxanüiden of the formula (I) according to claim 1, characterized in that

a) pyrazolylcarboxylic acid halides of the formula (II)

in which

X ¹ represents halogen,

with aniline derivatives of the formula (III)

in which

R ¹ represents halogen, cyano, nitro, C, -C ~ ₆ alkyl, C ₂ -C ₆ alkenyl, C, -C ₄ alkoxy, C, - C ₄ alkylthio, Ci-C ₄ alkylsulfonyl, C ₃ -C ₆ cycloalkyl, or ₄ -HaIo- genalkyl for Ci-C, _{Ci-C4-haloalkoxy,} _{Ci-C4-haloalkylthio} or C ₄ -HaIo- is genalkylsulfonyl each having 1 to 5 halogen atoms.

Halogenpyrazolecarboxariilides of the formula (IV)

in which

X ^{2 is} bromine or iodine,

with boronic acid derivatives of the formula (V)

"

in which R ¹ represents halogen, cyano, nitro, C _r C ₆ alkyl, C ₂ -C ₆ alkenyl, Ci-C ₄ alkoxy, C, - C ₄ alkylthio, Ci-C ₄ alkylsulfonyl, C ₃ -C ₆ -cycloalkyl, or for C ₁ -C ₄ -HaIo- genalkyl, Ci-C ₄ haloalkoxy, Ci-C ₄ haloalkylthio or CrC ₄ -HaIo- genalkylsulfonyl having in each case 1 to 5 halogen atoms and

G ¹ and G ^{2 are} each hydrogen or together are tetramethylethylene,

in the presence of a catalyst, or

Halogenpyrazolecarboxanilides of the formula (IV)

in which

X ^{2 is} bromine or iodine,

in a first stage with a diborane derivative of the Foπnel (VI)

G ⁴ - O _χ ^ -G ⁴ BB (VI)

₃ / \ ₃

G O O G ³

in which

G ³ and G ^{4 are} each alkyl or together are alkanediyl,

in which

R ¹ represents halogen, cyano, nitro, C _r C ₆ alkyl, C ₂ -C ₆ alkenyl, C _r C _.- alkoxy, Ci- C ₄ alkylthio, C _r C ₄ alkylsulfonyl, C ₃ -C ₆ -Cycloalkyl, or for Ci-C ₄ -HiIo-

5 genalkyl, dC ₄ haloalkoxy, C] -C ₄ haloalkylthio or -C ₄ -HaIo- genalkylsulfonyl having in each case 1 to 5 halogen atoms and

X ^{3 is} bromine, iodine or trifluoromethylsulfonyloxy,

in the presence of a catalyst.

8. An agent for controlling unwanted microorganisms comprising a 3-Difiuormethyl- 10 pyrazolylcarboxanilid according to any one of claims 1 to 6.

9. Use of 3-difluoromethyl-pyrazolylcarboxaniliden according to any one of claims 1 to 6 for controlling unwanted microorganisms.

10. A method for controlling unwanted microorganisms, characterized in that 3-difluoromethyl-pyrazolylcarboxanilide according to one of claims 1 to 6 to the

I ₅ microorganisms and / or their habitat brings.

11. A process for preparing agents for controlling unwanted microorganisms, characterized in that mixing 3-difluoromethyl-pyrazolylcarboxanilide according to any one of claims 1 to 6 with extenders and / or surface-active substances.