EP1881964A1 - Pyrazolocarboxamides as fungicides - Google Patents

Abstract

The invention relates to pyrazolocarboxamides of formula (I), where the variables have the following meanings: X = trifluoromethyl; R<SUP>1</SUP> = F, Cl, Br, C<SUB>1</SUB>-C<SUB>4</SUB> alkyl or C<SUB>1</SUB>-C<SUB>4</SUB>-haloalkyl, R<SUP>2 </SUP> = H, halogen or C<SUB>1</SUB>-C<SUB>4</SUB> alkyl, R<SUP>3</SUP> = H, C<SUB>1</SUB>-C<SUB>4</SUB> alkyl, C<SUB>1</SUB>-C<SUB>4</SUB> haloalkyl, C<SUB>2</SUB>-C<SUB>4</SUB> alkenyl, C<SUB>2</SUB>-C<SUB>4</SUB> alkinyl or C<SUB>3</SUB>-C<SUB>6</SUB> cycloalkyl; W = O or S with the proviso that when R<SUP>3</SUP> = H and W = O, a) R<SUP>1</SUP> methyl and R<SUP>2</SUP> F, b) R<SUP>1</SUP> trifluoromethyl and R<SUP>2</SUP> H or F, methods for production of said compounds means and seed stock containing the same and a method for prevention of fungal pests.

Description

 PYRAZOLEBOXYLIC ACID AMIDE AS FUNGICIDES

description

The present invention relates to pyrazolecarboxamides of the formula I.

in which the variables have the following meanings: X trifluoromethyl; R ¹ F ₁ Cl, bromine, -C ₄ alkyl or Ci-C ₄ haloalkyl; R ^{2 is} hydrogen, halogen or C 1 -C ₄ -alkyl; R ³ is hydrogen, -C ₄ alkyl, Ci-C ₄ haloalkyl, C ₂ -C ₄ alkenyl, C ₂ -C ₄ alkynyl, or

C ₃ -C ₆ cycloalkyl; W oxygen or sulfur,

with the proviso that when R ^{3 is} hydrogen and W is oxygen, then not simultaneously a) R ^{1 is} methyl and R ^{2 is} fluorine; b) R ^{1 is} trifluoromethyl and R ^{2 is} hydrogen or fluorine.

In addition, the invention relates to processes for the preparation of these compounds, compositions containing them and processes for their use for controlling harmful fungi.

From the literature Pyrazolcarbonsäureamide be known with fungicidal action. Thus, for example, EP-A 545 099 and EP-A 589 301 describe amides of the type of compounds I which have monosubstitution on the biphenyl group.

The general formula of the biocides described in JP-A 08/176112 likewise includes pyrazolecarboxamides having a monosubstituted biphenyl radical in the amide part.

WO 99/09013 and WO 00/14071 describe specific 1,3-dimethyl-5-fluoropyrazolecarboxamides and their fungicidal action. From JP-A 09/132567 pyrazolecarboxamides are known which have a specific 1 to 2-fold substitution in the biphenyl group and a trifluoromethyl group on the pyrazolyl group.

The object of the present invention was to find pyrazolecarboxamides with improved fungicidal activity in comparison with the compounds of the prior art.

Accordingly, the compounds I defined above were found.

In addition, there have been found processes for preparing these compounds, compositions containing them and methods of using them to control harmful fungi.

The compounds of the formula I can be present in various crystal modifications, which may differ in their biological activity. They are also the subject of the present invention.

The compounds I are generally obtained by reacting a carboxylic acid halide of the formula II in a manner known per se (for example J. March, Advanced Organic Chemistry, 2nd Ed., 382 f, McGraw-Hill, 1977) in the presence of a base with a

Aniline of formula III implements:

The radical Hal in the formula II represents a halogen atom such as fluorine, chlorine, bromine and iodine, in particular fluorine or chlorine. This reaction is usually carried out at temperatures of (-2O) ⁰ C to 100 ⁰ C, preferably O ⁰ C to 50 ° C.

Suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane and petroleum ether, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform and chlorobenzene, ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane , Anisole and tetrahydrofuran, nitriles such as acetonitrile and propionitrile, ketones such as acetone, methyl ethyl ketone, diethyl ketone and tert-butyl methyl ketone, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol and tert-butanol and also methylene chloride, dimethyl sulfoxide and dimethylformamide, more preferably toluene, methylene chloride and tetrahydrofuran.

It is also possible to use mixtures of the solvents mentioned.

Suitable bases are generally inorganic compounds such as alkali metal and alkaline earth metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide, alkali metal and alkaline earth metal oxides such as lithium oxide, sodium oxide, calcium oxide and magnesium oxide, alkali metal and alkaline earth metal hydrides such as lithium hydride, sodium hydride, potassium hydride and Calcium hydride, alkali metal amides such as lithium amide, sodium amide and potassium amide, alkali metal and alkaline earth metal carbonates such as lithium carbonate and calcium carbonate, and alkali metal hydrogencarbonates such as sodium bicarbonate and organometallic compounds, in particular alkali metal alkyls such as methyl lithium, butyl lithium and phenyllithium, alkyl magnesium halides such as methyl magnesium chloride and alkali metal and Erdaikalimetallalkoholate as Sodium methoxide, sodium ethoxide, potassium ethoxide, potassium tert-butoxide and Dimethoxymagnesium also organic bases, eg. B. tertiary amines such as trimethylamine, triethylamine, di-isopropylethylamine and N-methylpiperidine, pyridine, substituted pyridines such as collidine, lutidine and 4-dimethylaminopyridine and bicyclic amines into consideration.

Triethylamine and pyridine are particularly preferably used.

The bases are generally used in approximately equimolar amounts based on the compound Ii. But they can also be used in an excess of 5 mol% to 30 mol%, preferably 5 mol% to 10 mol%, or - in the case of using tertiary amines - optionally as a solvent.

The starting materials are generally reacted with one another in equimolar amounts. It may be advantageous for the yield to use II in an excess of 1 mol% to 20 mol%, preferably 1 mol% to 10 mol%, based on III.

The starting materials of the formulas II and III required for the preparation of the compounds I are known or can be synthesized analogously to the known compounds (HeIv.Chim.Acta, 60, 978 (1977); Zh. Org. Khim. 26, 1527 (1990 Heterocycles 26, 1885 (1987); Izv. Akad. Nauk, SSSR Ser. Khim., 2160 (1982); THL 28, 593 (1987); THL 29, 5463 (1988)).

It has furthermore been found that compounds of the formula I are obtained by reacting, in a known manner, carboxylic acids of the formula IV with an aniline of the formula III in the presence of dehydrating agents and, if desired, an organic base.

IV III

Suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane and petroleum ether, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform and chlorobenzene, ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane , Anisole and tetrahydrofuran, nitriles such as acetonitrile and propionitrile, ketones such as acetone, methyl ethyl ketone, diethyl ketone and tert-butyl methyl ketone, and dimethyl sulfoxide and dimethylformamide, more preferably methylene chloride, toluene and tetrahydrofuran.

It is also possible to use mixtures of the solvents mentioned.

Examples of suitable dehydrating agents are 1,1'-carbonyldiimidazole, bis (2-oxo-3-oxazolidinyl) phosphoryl chloride, carbodiimides, such as N, N'-dicyclohexylcarbodiimide, N- (3-dimethylaminopropyl) -N'-ethylcarbodiimide, and phosphonium salts, such as (benzotriazole). 1-yloxy) tris (dimethylamino) phosphonium hexafluorophosphate, bromotripyrrolidinophosphonium hexafluorophosphate, bromotris (dimethylamino) phosphonium hexafluorophosphate, chlorotripyrrolidinophosphonium hexafluorophosphate, uronium and thiuronium salts such as O- (benzotriazol-1-yl) -N, N, N ', N' tetramethyluronium hexafluorophosphate, O- (7-azabenzotriazoM-yl) -N, N, N \ N 4-tetramethyluronium hexafluorophosphate, S- (1-oxido-2-pyridyl) -N, N, N ¹ , N ¹ -tetramethylthiuronium tetrafluoroborate, O- (2- Oxo-1 (2H) pyridyl) - NNN'.N'-tetramethyluronium tetrafluoroborate, C4 (ethoxycarbonyl) cyano-methyleneamino] -N, N, N ', N'-tetramethyluronium tetrafluoroborate, carbenium salts such as (benzotriazole-1-ynyloxy) dipyrrolidinocarbenium hexafluorophosphate, ( Benzotriazol-1-yloxy) dipiperidinocarbenium hexafluoro phosphate, O- (3,4-dihydro-4-oxo-1,2,3-benzotriazine-S-yO-NNN'.N'-tetramethyluronium tetrafluoroborate, chloro-N ', N'-bis (tetramethylene) formamidinium tetrafluoroborate, chlorodipyrrolidinocarbenium hexafluorophosphate, chloro-N, N, N ', N'-bis (pentamethylene) formamidinium tetrafluoroborate, imidazolium salts such as 2-chloro-1,3-dimethylimidazolidinium tetrafluoroborate, preferably 1,1'-carbonyldiimidazole, bis (2-oxo-3-oxazolidinyl ) phosphoryl chloride, N, N'-dicyclohexylcarbodiimide and N- (3-dimethylaminopropyl) -N'-ethylcarbodiimide.

Suitable organic bases are, for example, tertiary amines such as trimethylamine, triethylamine, diisopropylethylamine and N-methylpiperidine, pyridine, substituted pyridines such as collidine, lutidine and 4-dimethylaminopyridine and also bicyclic amines. Triethylamine and pyridine are particularly preferably used. The bases will be in general in excess of 10 mol% to 200 mol%, preferably from 50 mol% to 150 mol%, based on the compound IV used.

The starting materials are generally reacted in approximately equimolar amounts with one another. It may be advantageous for the yield to use one of the compounds in an excess of 1 mol% to 20 mol%, preferably 1 mol% to 10 mol%. The dehydrating agents are generally used in excess of from 5 mol% to 100 mol%, preferably from 5 mol% to 60 mol%.

The starting materials of the formula III and IV required for the preparation of the compounds I are known or can be synthesized analogously to the known compounds.

The compounds I with R ³ ≠ hydrogen are preferably obtained by reacting compounds of the formula I where R ³ = H in a known manner in the presence of a base with an alkylating agent:

I (R ³ HH) ^alkyl ' ^{U U} »I I (R ³ = alkyl, haloalkyl, alkenyl, alkynyl, cycloalkyl); base

Suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane and petroleum ether, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform and chlorobenzene, ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane , Anisole and tetrahydrofuran, and also dimethyl sulfoxide and dimethylformamide, particularly preferably diethyl ether, tert-butyl methyl ether, tetrahydrofuran and dimethylformamide.

It is also possible to use mixtures of the solvents mentioned.

Suitable alkylating agents are, for example, alkyl halides such as methyl iodide, ethyl iodide, methyl bromide, ethyl bromide, methyl chloride and ethyl chloride, alkyl (perfluoroalkyl sulfonates) such as methyl trifluoromethyl sulfonate and ethyl trifluoromethyl sulfonate, alkyl (alkyl sulfonates) such as methyl methyl sulfonate and ethyl methyl sulfonate, alkyl (aryl sulfonates) such as methyl p-tolyl sulfonate and Ethyl p-tolylsulfonate, oxonium salts such as trimethyl oxonium tetrafluoroborate and triethyioxonium tetrafluoroborate.

Particularly preferred are methyl iodide, ethyl iodide, methyl bromide, ethyl bromide, methyl chloride and ethyl chloride.

Suitable bases are generally inorganic compounds such as alkali metal and alkaline earth metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide, alkali metal and alkaline earth metal oxides such as lithium oxide, sodium oxide, calzium oxide and magnesium oxide, alkali metal and alkaline earth metal hydrides such as lithium chloride, sodium hydride, potassium hydride and calcium hydride, alkali metal amides such as lithium amide, sodium amide and potassium amide, alkali metal and alkaline earth metal carbonates such as lithium carbonate, sodium carbonate, potassium carbonate and calcium carbonate and alkali metal hydrogen carbonates such as sodium hydrogencarbonate, organometallic compounds, especially alkali metal alkyls such as methyllithium, butyllithium and phenyllithium , Alkylmagnesiumhalogenide such as methylmagnesium chloride and alkali metal and Erdalkalimetallalkoholate such as sodium, sodium, potassium and potassium tert-butoxide in consideration.

Particular preference is given to using sodium carbonate, potassium carbonate, sodium hydride, potassium hydride, butyllithium and potassium tert-butoxide.

The bases are generally used in approximately equimolar amounts, based on the compound I. However, they can also be used in an excess of 5 mol% to 30 mol%, preferably 5 mol% to 10 mol%.

The starting materials are generally reacted with each other in approximately equimolar amounts. It may be advantageous for the yield to use the alkylating agent in an excess of 1 mol% to 20 mol%, preferably 1 mol% to 10 mol%, based on I.

Those pyrazolecarboxamides I ₁ in which W is sulfur can be prepared, for example, by sulfurization of the corresponding compounds I in which X is oxygen (cf., for example, D. Petrova & K. Jakobcic, Croat. Chem. Acta 48, 49 (1976 ) and WO 01/42223).

With regard to their use in fungicidal agents, compounds of the formula I are suitable in which the substituents have the following meaning:

Halogen is fluorine, chlorine, bromine or iodine;

C 1 -C ₄ -alkyl is methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl or 1, 1-dimethylethyl;

C ₁ -C ₄ -haloalkyl represents a partially or completely halogenated C ₁ -C ₄ -alkyl radical, where the halogen atom (s) is / are in particular fluorine, chlorine and / or bromine, ie, for example, chloromethyl, bromomethyl, dichloromethyl, Trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2-chloro-2-fluoroethyl, 2,2, 2-trifluoroethyl, 2-chloro, 1,2-trifluoroethyl, 2-chloro-2,2-difluoroethyl, 2-bromo-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2- Trichloroethyl, 1,1,2,2-tetrafluoroethyl, 1,1,2,2-tetrachloroethyl, pentafluoroethyl, 2,2,3,3-tetrafluoromopropyl, 1,1,3,3,3,3- Hexafluoro-1-propyl, 1,1,1,3,3,3-hexafluoro-2-propyl, heptafluoro-1-propyl, heptafluoro-2-propyl, 2,2,3,3,4,4,4- Heptafluoro-1-butyl or nonafluoro-1-butyl, in particular for halomethyl, particularly preferably for CH ₂ -CI, CH (Cl) ₂ , CH ₂ -F, CH (F) ₂ , CF ₃ , CHFCl, CF ₂ Cl or CF (CI) ₂ ;

C ₂ -C ₄ alkenyl is a straight-chain or branched hydrocarbon radical having 2, 3 or 4 carbon atoms and one or two double bonds, for example vinyl, allyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl , 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl or 2-methyl-2-propenyl, in particular for allyl;

C ₂ -C ₄ -alkynyl is a straight-chain or branched hydrocarbon radical having 2, 3 or 4 carbon atoms and a triple bond, for example ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl or i-methyl-2-propynyl, in particular ethynyl, 1-propynyl or 2-propynyl;

_C3-C6 cycloalkyl is cyclopropyl, cyclobutyl; Cyclopentyl or cyclohexyl.

With regard to the biological activity of the compounds I, the following meanings of the variables are preferred, each alone or in combination: R ^{1 is} fluorine, chlorine, methyl, fluoromethyl, difluoromethyl, chlorofluoromethyl, chlorodifluoromethyl, dichlorofluoromethyl or trifluoromethyl preferably methyl, fluoromethyl, difluoromethyl, chlorofluoromethyl or trifluoromethyl, in particular difluoromethyl or trifluoromethyl, very particularly preferably difluoromethyl; R ^{2 is} hydrogen, fluorine, chlorine or methyl, particularly preferably hydrogen, fluorine or chlorine, in particular hydrogen or chlorine, very particularly preferably hydrogen; R ^{3 is} hydrogen, methyl or ethyl, particularly preferably hydrogen or methyl, in particular hydrogen; W oxygen.

Particular preference is given to compounds I having the following substituent combinations, in which the variables have the following meanings:

R ^{1 is} fluorine, chlorine, methyl, fluoromethyl, difluoromethyl, chlorofluoromethyl, chlorodifluoromethyl, dichlorofluoromethyl or trifluoromethyl, in particular fluorine, chlorine, fluoromethyl, difluoromethyl, chlorofluoromethyl, chlorodifluoromethyl, dichlorofluoromethyl or trifluoromethyl, very particularly preferably fluorine, chlorine, fluoromethyl, difluoromethyl, Chlorofluoromethyl, chlorodifluoromethyl or dichlorofluoromethyl;

R ^{2 is} hydrogen, fluorine, chlorine or methyl, in particular hydrogen, fluorine or chlorine, very particularly preferably hydrogen or chlorine;

R ^{3 is} hydrogen, methyl or ethyl, in particular hydrogen or methyl, very particularly preferably hydrogen; W oxygen.

Also preferred are combinations of substituents having the following meanings: R ^{1 is} fluorine, chlorine, methyl, fluoromethyl, difluoromethyl, chlorofluoromethyl, or chlorodifluoromethyl; R ^{2 is} hydrogen, fluorine, chlorine or methyl, in particular hydrogen, fluorine or

Chlorine, most preferably hydrogen or chlorine;

R ^{3 is} hydrogen, methyl or ethyl, particularly preferably hydrogen or methyl, in particular hydrogen;

W oxygen.

Also preferred are combinations of substituents having the following meanings: R ^{1 is} fluoromethyl, difluoromethyl, chlorofluoromethyl or dichlorofluoromethyl, in particular difluoromethyl, chlorofluoromethyl or dichlorofluoromethyl, very particularly preferably difluoromethyl; R ^{2 is} hydrogen, fluorine, chlorine or methyl, in particular hydrogen, fluorine or

Chlorine, very particularly preferably hydrogen; R ^{3 is} hydrogen, methyl or ethyl, in particular hydrogen; W oxygen.

Particular preference is also given to compounds I ₁ in which R ^{1 is} methyl, R ^{2 is} hydrogen, chlorine or methyl, in particular hydrogen or chlorine, R ^{3 is} hydrogen, methyl or ethyl, in particular hydrogen, and W is oxygen.

Particular preference is also given to compounds I in which R ^{1 is} trifluoromethyl, R ^{2 is} chlorine or methyl, in particular chlorine, R ^{3 is} hydrogen, methyl or ethyl, in particular hydrogen, and W is oxygen.

An embodiment of the invention consists in the provision of Pyrazolcarbon- acid amides I with X in the ortho position (= compounds Ia):

A further embodiment of the invention consists in the provision of pyrazolecarboxamides I with X in the meta position (= compounds Ib):

A further embodiment of the invention consists in the provision of pyrazolecarboxamides I with X in the para position (= compounds Ic):

In particular, in view of their use as fungicides, the compounds of general formula I-A are preferred.

(I-A)

Table A

Table 1 :

Compounds of the general formula IA in which R ² and R ^{3 are} hydrogen and R ¹ and B for each individual compound correspond in each case to one row of Table A, with the exception of rows 1 to 3.

Table 2:

Compounds of the general formula IA in which R ^{2 is} chlorine and R ^{3 is} hydrogen and R ¹ and B for each individual compound correspond in each case to one row of Table A.

Table 3:

Compounds of the general formula IA in which R ^{2 is} fluorine and R ^{3 is} hydrogen and R ¹ and B for each individual compound correspond in each case to one row of Table A, with the exception of rows 1 to 3 and 19 to 21.

Table 4:

Compounds of the general formula IA in which R ^{2 is} hydrogen and R ^{3 is} methyl and R ¹ and B for each individual compound correspond in each case to one row of Table A.

Table 5:

Compounds of the general formula IA in which R ^{2 is} hydrogen and R ^{3 is} ethyl and R ¹ and B for each individual compound correspond in each case to one row of Table A. Very particular preference is given to the following pyrazolecarboxamides of the formula I: 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid N- (4'-trifluoromethylbiphenyl-2-yl) -amide, 3-difluoromethyl-1-methyl- 1 H-pyrazole-4-carboxylic acid N- (3'-trifluoromethylbiphenyl-2-yl) -amide, 3-difluoromethyl-1-methyl-1 H-pyrazole-4-carboxylic acid N- (2'-trifluoromethylbiphenyl -2-yl) -amide, 5-chloro, 3-dimethyl-1H-pyrazole-4-carboxylic acid N- (4'-trifluoromethyl-biphenyl-2-yl) -amide, 1, 3-dimethyl-1H pyrazole-4-carboxylic acid N- (4'-trifluoromethyl-biphenyl-2-yl) -amide, 3-fluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid N- (4'-trifluoromethylbiphenyl -2-yl) amide, 3-chlorodifluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid N- (4'-trifluoromethylbiphenyl-2-yl) -amide and 3-chlorofluoromethyl-1-methyl-1H pyrazole-4-carboxylic acid N- (4'-trifluoromethylbiphenyl-2-yl) -amide.

The compounds I are suitable as fungicides. They are distinguished by outstanding activity against a broad spectrum of phytopathogenic fungi, in particular from the classes of the Ascomycetes, Deuteromycetes, Oomycetes and Bassidiomycetes. They are partially systemically effective and can be used in crop protection as foliar, pickling and soil fungicides.

They are particularly important for the control of a large number of fungi on various crops such as wheat, rye, barley, oats, rice, maize, grass, bananas, cotton, soy, coffee, sugar cane, wine, fruit and ornamental plants and vegetables such as Cucumbers, beans, tomatoes, potatoes and cucurbits, as well as the seeds of these plants.

In particular, they are suitable for controlling the following plant diseases: Alternaria species on vegetables, oilseed rape, sugar beets and fruits and rice, e.g. A. so / an / or A. alternata on potatoes and tomatoes,

Aphanomyces species of sugar beets and vegetables,

Ascochyta species on cereals and vegetables,

Bipolaris and Drechslera species on corn, cereals, rice and turf, e.g. D. maydis on corn,

Blumeria graminis (powdery mildew) on cereals,

Botrytis cinerea (gray mold) on strawberries, vegetables, flowers and vines,

Bremia lactucae on salad,

Cercospora species on corn, soybeans, rice and sugar beets, - Cochliobolus species on maize, cereals, rice, e.g. Cochliobolus sativus on cereals,

Cochliobolus miyabeanus on rice,

Colletotricum species on soybeans and cotton,

Drechslera species, Pyrenophora species on corn, cereals, rice and turf, e.g. D. teres to barley or D. tritici-repentis to wheat, - Esca to grapevine, caused by Phaeoacremonium chlamydosporium, Ph.

Aleophilum and Formitipora punctata (syn. Phellinus punctatus),

Exserohilum species on corn, Erysiphe cichoracearum and Sphaerotheca fullginea on cucurbits,

Fusarium and Verticillium species on various plants, e.g. F. graminearum or F. culmorum on cereal or F. oxysporum on a variety of plants, e.g. Tomatoes, - Gaeumanomyces graminis on cereals,

Gibberella species on cereals and rice (e.g., Gibberella fujikuroi on rice),

Grainstaining complex on rice,

Helminthosporium species on corn and rice,

Michrodochium nivale on cereals, - Mycosphaerella species on cereals, bananas and peanuts, e.g. A /. graminicola on wheat or M / ps> s / s on bananas,

Peronospora A anen on cabbage and bulbous plants, e.g. P. brassicae on cabbage or P. destructor on onion,

Phakopsara pachyrhizi and Phakopsara meibomiae on soybeans, - Phomopsis species on soybeans and sunflowers,

Phytophthora infestans on potatoes and tomatoes,

Phytophthora species on various plants, e.g. / °. capsici with peppers,

Plasmopara viticola on vines,

Podosphaera leucotricha on apple, - Pseudocercosporella herpotrichoides on cereals,

Pseudoperonospora on various plants, e.g. F. cubensis on cucumber or

P. humili on hops,

Puccinia species on various plants, e.g. P. triticina, P. striformins, P. hordei or P. graminis on cereals or P. asparagi on asparagus, - Pyricυlaria oryzae, Corticium sasakii, Sarocladium oryzae, S. attenuatum, Entlyoma oryzae on rice,

Pyricularia grisea on lawn and cereals,

Pythium spp. on turf, rice, corn, cotton, oilseed rape, sunflowers, sugar beets, vegetables and other plants, e.g. P. ultiumum on different plants, P. aphanidermatum on grass,

Rhizoctonia species on cotton, rice, potatoes, turf, corn, rapeseed, sugar beets, vegetables and on various plants, e.g. R. solani on turnips and various plants,

Rhynchosporium secalis on barley, rye and triticale, - Sclerotinia species on oilseed rape and sunflowers,

Septoria tritici and Stagonospora nodorum on wheat,

Erysiphe (Syn. Uncinula) necator on grapevine,

Setospaeria species on corn and turf,

Sphacelotheca reilinia on maize, - Thievaliopsis species on soybeans and cotton,

Tilletia species of cereals,

Ustilago species on cereals, maize and sugarcane, eg U. maydis on maize, Venturia species (scab) on apples and pears, eg V. inaequalis on apple.

In particular, the compounds I are suitable for controlling harmful fungi from the class of the Peronosporomycetes (syn. Oomycetes), such as Peronospora plants, Phytophthora plants, Plasmopara viticola, Pseudoperonospora arias and Pythium species.

The compounds I are also suitable for controlling harmful fungi in the protection of materials (for example wood, paper, paint dispersions, fibers or fabrics) and in the protection of stored products. In wood preservation, particular attention is paid to the following harmful fungi: Ascomycetes such as Ophiostoma spp., Ceratocystis spp., Aureobasidi um pullulans, Sciérophoma spp., Chaetomium spp., Humicola spp., Petriella spp., Trichurus spp .; Basidiomycetes such as Coniophora spp., Coriolus spp., Gloeophyllum spp., Lentinus spp., P / et / -AoΛ / sspp., Por / a spp., Serpula spp. and Tyomyces spp., Deuteromycetes such as Aspergillus spp., Cladosporium spp., Penicillium spp., Trichoderma spp., Alternaria spp., Paecilomyces spp. and Zygomycetes such as Mucor spp., moreover, in the protection of the following yeasts: Candida spp. and Saccharomyces cerevisae.

The compounds I are used by treating the fungi or the plants, seeds, materials or the soil to be protected against fungal attack with a fungicidally effective amount of the active ingredients. The application can be done both before and after the infection of the materials, plants or seeds by the fungi.

The fungicidal compositions generally contain from 0.1 to 95, preferably 0.5 to 90 wt .-% of active ingredient.

The application rates in the application in crop protection, depending on the nature of the desired effect at 0.01 to 2.0 kg of active ingredient per hectare.

In seed treatment, in general, amounts of active ingredient of 1 g to 1000 g per 100 kg, preferably 5 g to 100 g per 100 kg of seed are needed.

When used in material or storage protection, the application rate of active ingredient depends on the type of application and the desired effect. Usual application rates are, for example, 0.001 g to 2 kg, preferably 0.005 g to 1 kg of active ingredient per cubic meter of material treated in the material protection.

The compounds I can be converted into the customary formulations, for example solutions, emulsions, suspensions, dusts, powders, pastes and granules. The application form depends on the respective purpose; In any case, it should ensure a fine and uniform distribution of the compound according to the invention. The formulations are prepared in a known manner, for example by stretching the active ingredient with solvents and / or excipients, if desired using emulsifiers and dispersants. Solvents / auxiliaries which are suitable are essentially: - water, aromatic solvents (for example Solvesso ^® products, xylene) ₁ paraffins (for example mineral oil fractions), alcohols (for example methanol, butanol, pentanol, benzyl alcohol), keto ne (for example cyclohexanone, gamma-butyrolactone), pyrrolidones (N-methylpyrrolidone, N-octylpyrrolidone), acetates (glycol diacetate), glycols, dimethyl fatty acid amides, fatty acids and fatty acid esters. In principle, solvent mixtures can also be used.

Excipients such as ground natural minerals (e.g., kaolins, clays, talc, chalk) and ground synthetic minerals (e.g., fumed silica, silicates); Emulsifiers such as nonionic and anionic emulsifiers (e.g., polyoxyethylene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates) and dispersants such as lignin liquors and methyl cellulose.

The surface-active substances used are alkali metal, alkaline earth metal, ammonium salts of lignin sulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutylnaphthalenesulfonic acid, alkylarylsulfonates, alkyl sulfates, alkyl sulfonates, fatty alcohol sulfates, fatty acids and sulfated fatty alcohol glycol ethers, and condensation products of sulfonated naphthalene and naphthalene derivatives with formaldehyde , Condensation products of naphthalene or naphthalenesulfonic acid with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers, tristerylphenyl polyglycol ethers, alkylaryl polyether alcohols, alcohol and fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene , Laurylalkoholpoly- glycol ether acetal, sorbitol esters, Ligninsulfitablaugen and methyl cellulose into consideration.

For the preparation of directly sprayable solutions, emulsions, pastes or oil dispersions, there are mineral oil fractions of medium to high boiling point, such as kerosine or diesel oil, coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. Toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone, strong polar solvents, e.g. Dimethylsulfoxide, N-methylpyrrolidone or water into consideration.

Powders, dispersants and dusts may be prepared by mixing or co-grinding the active substances with a solid carrier.

Granules, for example coated, impregnated and homogeneous granules, can be prepared by binding the active compounds to solid carriers. Solid carriers are, for example, mineral earths, such as silica gels, silicates, talc, kaolin, attaclay, limestone, Lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers, eg ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and vegetable products, such as cereal flour, tree bark, wood and nutshell flour, cellulose powder and other solid carriers.

The formulations generally contain from 0.01 to 95 wt .-%, preferably 0.1 to 90 wt .-%, of at least one active ingredient I. The active ingredients are in a purity of 90% to 100%, preferably 95% to 100%, (according to NMR spectrum) used.

Examples of formulations are: 1. Products for dilution in water

A Water-soluble concentrates (SL, LS) 10 parts by weight of a compound I according to the invention are mixed with 90 parts by weight

Dissolved in water or a water-soluble solvent. Alternatively, wetting agents or other adjuvants are added. When diluted in water, the active ingredient dissolves. This gives a formulation with 10 wt .-% active ingredient content.

B Dispersible Concentrates (DC)

20 parts by weight of a compound I according to the invention are dissolved in 70 parts by weight of cyclohexanone with the addition of 10 parts by weight of a dispersant, e.g. Polyvinylpyrrolidone, dissolved. Dilution in water gives a dispersion. The active ingredient content is 20% by weight.

C Emulsifiable Concentrates (EC)

15 parts by weight of a compound I according to the invention are dissolved in 75 parts by weight of xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight). Dilution in water results in an emulsion. The formulation has 15% by weight active ingredient content.

D emulsions (EW, EO, ES)

25 parts by weight of a compound I according to the invention are dissolved in 35 parts by weight of xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight). This mixture is added by means of an emulsifier (Ultraturrax) in 30 parts by weight of water and brought to a homogeneous emulsion. Dilution in water results in an emulsion. The formulation has an active ingredient content of 25% by weight.

E suspensions (SC, OD, FS)

20 parts by weight of a compound I according to the invention are mixed with the addition of 10 parts by weight of dispersants and wetting agents and 70 parts by weight of water or an organic compound. nischen solvent in a stirred ball mill to a fine active ingredient suspension comminuted. Dilution in water results in a stable suspension of the active ingredient. The active ingredient content in the formulation is 20% by weight.

F Water-dispersible and water-soluble granules (WG, SG)

50 parts by weight of a compound I according to the invention are finely ground with the addition of 50 parts by weight of dispersants and wetting agents and prepared by means of industrial equipment (for example extrusion, spray tower, fluidized bed) as water-dispersible or water-soluble granules. Dilution in water results in a stable dispersion or solution of the active ingredient. The formulation has an active ingredient content of 50% by weight.

G Water-dispersible and water-soluble powders (WP, SP, SS ₁ WS) 75 parts by weight of a compound I according to the invention are ground in a rotor-stator mill with the addition of 25 parts by weight of dispersing and wetting agents and silica gel. Dilution in water results in a stable dispersion or solution of the active ingredient. The active ingredient content of the formulation is 75% by weight.

H Gel Formulations (GF) In a ball mill 20 parts by weight of a compound 1, 10

Parts by weight of dispersant, 1 part by weight of swelling agent ("gelling agent") and 70 parts by weight

Grind water or an organic solvent to a fine suspension.

Dilution with water gives a stable suspension with 20% by weight.

Drug content.

2. Products for direct application

J dusts (DP, DS)

5 parts by weight of a compound I according to the invention are finely ground and intimately mixed with 95 parts by weight of finely divided kaolin. This gives a dust with 5 wt .-% active ingredient content.

K Granules (GR, FG, GG, MG)

0.5 part by weight of a compound I according to the invention are finely ground and combined with 99.5 parts by weight of carriers. Common processes are extrusion, spray drying and fluidized bed. This gives a granulate for direct application with 0.5 wt .-% active ingredient content.

L ULV solutions (UL) 10 parts by weight of a compound I according to the invention are dissolved in 90 parts by weight of an organic solvent, for example xylene. This gives a product for direct application with 10 wt .-% active ingredient content. For seed treatment, water-soluble concentrates (LS), suspensions (FS), dusts (DS), water-dispersible or water-soluble powders (WS, SS), emulsions (ES), emulsifiable concentrates (EC) and gel formulations (GF) are usually used. These formulations can be applied to the seed undiluted or, preferably, diluted. The application can be done before sowing.

The active compounds may be used as such, in the form of their formulations or the forms of use prepared therefrom, e.g. in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, scattering agents, granules by spraying, misting, dusting, scattering or pouring. The forms of application depend entirely on the intended use; In any case, they should ensure the finest possible distribution of the active compounds I according to the invention.

Aqueous application forms can be prepared from emulsion concentrates, pastes or wettable powders (wettable powders, oil dispersions) by adding water. To prepare emulsions, pastes or oil dispersions, the substances, as such or dissolved in an oil or solvent, can be homogenized in water by means of wetting agents, tackifiers, dispersants or emulsifiers. But it can also be made of effective substance wetting, adhesion, dispersing or emulsifying and possibly solvent or oil concentrates, which are suitable for dilution with water.

The active compound concentrations in the ready-to-use preparations can be varied within wide ranges. In general, they are 0.0001 to 10%, preferably 0.01 to 1%.

The active ingredients can also be used with great success in the ultra-low-volume (ULV) process, it being possible to apply formulations containing more than 95% by weight of active ingredient or even the active ingredient without additives.

To the active ingredients oils of various types, wetting agents, adjuvants, herbicides, fungicides, other pesticides, bactericides, optionally also just before use (tank mix), are added. These agents are usually admixed to the compositions according to the invention in a weight ratio of 1: 100 to 100: 1, preferably 1:10 to 10: 1.

Particularly suitable adjuvants in this sense are: organically modified polysiloxanes, eg, Break Thru, p. ^240® ; Alcohol alkoxylates such as Atplus 245 ^®, Atplus MBA 1303 ^®, Plurafac ^® LF 300 and Lutensol ^® ON 30; EO-PO block polymers, eg Pluronic RPE 2035 ^® and Genapol B ^®; Alkoholethxylate, eg Lutensol ^® XP80; and sodium dioctylsulfosuccinate, for example Leophen ^® RA.

The agents according to the invention may also be present in the form of use as fungicides together with other active substances, e.g. with herbicides, insecticides, growth regulators such as Prohexadion Ca, fungicides or with fertilizers. When mixing the compounds I or the agents containing them with one or more further active compounds, in particular fungicides, for example, in many cases, the spectrum of activity can be broadened or development of resistance can be prevented. In many cases, synergistic effects are obtained.

The following list of fungicides with which the compounds of the invention can ^'be used is intended to illustrate the possible combinations but does not limit:

strobilurins

Azoxystrobin, dimoxystrobin, enestroburine, fluoxastrobin, kresoxim-methyl, metominostrobin, picoxystrobin, pyraclostrobin, trifloxystrobin, orysastrobin, (2-chloro-5- [1- (3-methyl-benzyloxyimino) -ethyl] -benzyl) -carbamic acid methyl ester, (2-Chloro-5- [1- (6-methylpyridin-2-ylmethoxyimino) ethyl] benzyl) -carbamic acid methyl ester, 2- (ortho- (2,5-dimethylphenyl-oxymethylene) -phenyl) -3- methoxy-methyl acrylate;

carboxamides

- Carboxylic acid anilides: benalaxyl, benodanil, boscalid, carboxin, mepronil, fenfuram, fenhexamide, flutolanil, furametpyr, metalaxyl, ofurace, oxadixyl, oxycarboxin,

Penthiopyrad, thifluzamide, tiadinil, 4-difluoromethyl-2-methyl-thiazole-5-carboxylic acid (4'-bromo-biphenyl-2-yl) -amide, 4-difluoromethyl-2-methyl-thiazole-5-carboxylic acid - (4'-trifluoromethyl-biphenyl-2-yl) -amide, 4-difluoromethyl-2-methyl-thiazole-5-carboxylic acid (4'-chloro-3'-fluoro-biphenyl-2-yl) - amide, 3-Difluoromethyl-1-methyl-pyrazole-4-carboxylic acid (3 ', 4'-dichloro-4-fluoro-biphenyl-2-yl) -amide, 3,4-dichloro-isothiazole-5 carboxylic acid (2-cyano-phenyl) -amide;

- Carboxylic acid morpholides: Dimethomorph, Flumorph;

Benzoic acid amides: flumetover, fluopicolide (picobenzamide), zoxamide;

Other carboxamides: carpropamide, diclocymet, mandipropamide, N- (2- (4- [3- (4-chloro-phenyl) -prop-2-ynyloxy] -3-methoxyphenyl) -ethyl) -2-methanesulfonylamino

3-methyl-butyramide, N- (2- (4- [3- (4-chloro-phenyl) -prop-2-ynyloxy] -3-methoxy-phenyl) -ethyl) -2-ethanesulfonyl-amino-3-methyl- butyramide;

Azoles - triazoles: bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, enilconazole, epoxiconazole, fenbuconazole, flusilazole, fluquinconazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, penconazole, Propiconazole, prothioconazole, simecoπazole, tebuconazole, tetraconazole, triadimol, triadimefon, triticonazole;

- imidazoles: cyazofamide, imazalil, pefurazoate, prochloraz, triflumizole;

Benzimidazoles: benomyl, carbendazim, fuberidazole, thiabendazole; - Other: ethaboxam, etridiazole, hymexazole;

Nitrogen-containing heterocyclyl compounds

Pyridines: fluazinam, pyrifenox, 3- [5- (4-chlorophenyl) -2,3-dimethylisoxazolidin-3-yl] pyridine; Pyrimidines: bupirimate, cyprodinil, ferimzone, fenarimol, mepanipyrim, nuarimol, pyrimethanil;

- piperazine: triforin;

- Pyrroles: fludioxonil, fenpiclonil;

- Morpholines: aldimorph, dodemorph, fenpropimorph, tridemorph; Dicarboximides: iprodione, procymidone, vinclozolin;

- others: AcibenzoIar-S-methyl, anilazine, captan, captafol, dazomet, diclomethine, fenoxanil, folpet, fenpropidin, famoxadone, fenamidone, octhilinone, probenazole, proquinazide, pyroquilon, quinoxyfen, tricyclazole, 5-chloro-7- (4- methyl-piperidin-1-yl) -6- (2,4,6-trifluorophenyl) - [1, 2,4] triazolo [1,5-a] pyrimidine, 2-butoxy-6-iodo-3- propylchromen-4-one, 3- (3-bromo-6-fluoro-2-methyl-indole-1-sulfonyl) - [1, 2,4] triazole-1-sulfonic acid dimethylamide;

Carbamates and dithiocarbamates

Dithiocarbamates: Ferbam, Mancozeb, Maneb, Metiram, Metam, Propineb, Thiram, Zineb, Ziram;

Carbamates: diethofencarb, flubenthiavalicarb, iprovalicarb, propamocarb, 3- (4-chlorophenyl) -3- (2-isopropoxycarbonylamino-3-methyl-butyrylamino) -propionic acid methyl ester, N- (1 - (1 - (4- cyanophenyl) ethanesulfonyl) -but-2-yl) carbamic acid (4-fluorophenyl) ester;

Other fungicides

- guanidines: dodine, iminoctadine, guazatine;

- Antibiotics: Kasugamycin, Polyoxins, Streptomycin, Validamycin A;

Organometallic compounds: fentin salts; Sulfur-containing heterocyclyl compounds: isoprothiolanes, dithianone;

Organophosphorus compounds: edifenphos, fosetyl, fosetyl-aluminum, Iprobenfos, pyrazophos, tolclofos-methyl, phosphorous acid and their salts;

Organochlorine compounds: thiophanate methyl, chlorothalonil, dichlofluanid, toluidanide, flusulfamide, phthalide, hexachlorobenzene, pencycuron, quintozene; Nitrophenyl derivatives: binapacryl, dinocap, dinobuton;

- Inorganic active substances: Bordeaux broth, copper acetate, copper hydroxide, copper oxychloride, basic copper sulphate, sulfur; Other: Spiroxamine, Cyflufenamid, Cymoxanil, Metrafenon.

synthesis Examples

Example 1 :

3-Difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid N- (4'-trifluoromethylbiphenyl-2-yl) -amide (Compound 1.1): 0 To a solution of 0.36 g of 4'-trifluoromethyl- 2-Aminobiphenyl and 0.18 g of pyridine in 10 ml of toluene were added dropwise at room temperature 0.29 g of 3-difluoromethyl-1-methyl-1 Mpyrazol- 4-carboxylic acid chloride, after which the mixture was stirred for 16 hours at room temperature. 30 ml of methyl-Fe / t.-butyl ether were added and the organic phase was washed successively with 2% hydrochloric acid, 2% sodium hydroxide solution and then 5 with dilute aqueous sodium chloride solution. The organic phase was dried and concentrated in vacuo. The crude product was stirred with 5 ml of diisopropyl ether. The residual solid was separated and dried. This gave 0.45 g of the desired product as a white powder; Mp 164-165 ° C.

Q According to the instructions given here, the compounds of the formula I indicated in Table 6 below were prepared with W = O.

Table 6

5

applications

The active compounds were prepared as a stock solution containing 25 mg of active ingredient I, which with a mixture of acetone and / or dimethyl sulfoxide and the emulsifier Uni- perol ^® EL (ethoxylated wetting agent having emulsifying and dispersing action based on alkylphenols) in a volume ratio solvent / Emulsifier from 99 to 1 ad 10 ml was filled up. It was then made up to 10 ml with water. This stock solution was diluted with the described solvent / emulsifier / water mixture to the drug concentration given below.

Protective activity against Puccinia recondΛ ^' a on wheat (wheat brown rust)

Leaves of potted wheat seedlings of the variety "Chancellor" were sprayed to drip point with an aqueous suspension in the active ingredient concentration given below. The next day, the treated plants were inoculated with a spore suspension of the wheat brown rust {Puccinia recondita). Subsequently, the plants were placed in a high humidity chamber (90 to 95%) at 20 to 22 ° C for 24 hours. During this time, the spores germinated and the germ tubes penetrated into the leaf tissue. The following day, the test plants were returned to the greenhouse and cultured at temperatures between 20 and 22 ⁰ C and 65 to 70% relative humidity for a further 7 days. Then the extent of rust fungus development on the leaves was visually determined.

In this test, the plants treated with 250 ml of the compounds 1.1, 1.2 and I.3 from Table 6 showed a maximum of 7% infestation, while the untreated plants were 90% infected.

Efficacy against the net blotch of barley caused by Pyrenophora teres at 1 day of protective application

Leaves of potted barley seedlings were sprayed to drip point with aqueous suspension in the concentration of active compound given below. 24 hours after the spray coating had dried on, the test plants were incubated with an aqueous spore suspension of Pyrenophora [syn. Drechslera] teres, the causative agent of net blotch inoculation. Subsequently, the test plants were placed in a greenhouse at temperatures between 20 and 24 ⁰ C and 95 to 100% relative humidity. After 6 days, the extent of disease development was determined visually as% of total leaf area.

In this test, the plants treated with 250 ml of the compounds 1.1, 1.2 and I.3 from Table 6 showed a maximum of 7% infestation, while the untreated plants were 90% infected.

Claims

 claims

1. pyrazolecarboxamides of the formula I.

in which the variables have the following meanings:

X is trifluoromethyl;

R ¹ F ₁ Cl, bromine, C _r C ₄ alkyl or -C ₄ haloalkyl;

R ^{2 is} hydrogen, halogen or C 1 -C ₄ -alkyl;

R ³ is hydrogen, -C ₄ alkyl, CrC ₄ -Haiogenalkyl, C ₂ -C ₄ alkenyl, C ₂ -C ₄ alkynyl, or C3-C6 cycloalkyl; W is oxygen or sulfur, with the proviso that when R ^{3 is} hydrogen and W is oxygen, then not simultaneously a) R ^{1 is} methyl and R ^{2 is} fluorine; b) R ^{1 is} trifluoromethyl and R ^{2 is} hydrogen or fluorine.

Pyrazolecarboxamides of the formula I according to Claim 1, in which the variables have the following meanings:

R ^{1 is} F, chlorine, methyl, fluoromethyl, difluoromethyl, chlorofluoromethyl, chlorodifluoromethyl, dichlorofluoromethyl or trifluoromethyl; R ^{2 is} hydrogen, F, Cl or methyl; R ^{3 is} hydrogen or methyl; W oxygen.

Pyrazolecarboxamides of the formula I according to Claim 1, in which the variables have the following meanings:

R ^{1 is} F, Cl, methyl, fluoromethyl, difluoromethyl, chlorofluoromethyl, chlorodifluoromethyl, dichlorofluoromethyl or trifluoromethyl; R ^{2 is} hydrogen, F or chlorine; R ^{3 is} hydrogen; W oxygen.

4. pyrazolecarboxamides of the formula I according to claim 1, in which the variables have the following meanings:

R ¹ F ₁ Cl, methyl, fluoromethyl, difluoromethyl, chlorofluoromethyl, chlorodifluoro- methyl, dichlorofluoromethyl or trifluoromethyl; R ^{2 is} hydrogen or chlorine; R ^{3 is} hydrogen; W oxygen;

5. pyrazolecarboxamides of the formula I according to claim 1, in which the variables have the following meanings:

R ^{1 is} fluorine, chlorine, fluoromethyl, difluoromethyl, chlorofluoromethyl, chlorodifluoromethyl or dichlorofluoromethyl; R ^{2 is} hydrogen, fluorine, chlorine or methyl;

R ^{3 is} hydrogen, methyl or ethyl; W oxygen;

6. Pyrazolcarbonsäureamide of the formula I according to claim 1, in which the variables have the following meanings:

R ^{1 is} methyl;

R ^{2 is} hydrogen, chlorine or methyl; R ^{3 is} hydrogen, methyl or ethyl; W oxygen;

7. Pyrazolcarbonsäureamide of the formula I according to claim 1, in which the variables have the following meanings:

R ¹ trifluoromethyl;

R ^{2 is} chlorine or methyl; R ^{3 is} hydrogen, methyl or ethyl;

W oxygen;

8. Pyrazolcarbonsäureamide of the formula I according to claim 1, selected from the group consisting of 3-difluoromethyl-1-methyl-1 H-pyrazole-4-carboxylic acid N- (4'-trifluoromethylbiphenyI-2-yl) -amide, 3- Difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid N- (3'-trifluoromethyl-biphenyl-2-yl) -amide, 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid N- (2 '-trifluoromethylbiphenyl-2-yl) amide, 5-chloro-1,3-dimethyl-1H-pyrazole-4-carboxylic acid N- (4'-trifluoromethylbiphenyl-2-yl) -amide, 1,3-dimethyl -1H-pyrazole-4-carboxylic acid N- (4'-trifluoromethyl-biphenyl-2-yl) -amide, 3-fluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid N- (4'-trifluoromethyl-biphenyl-2 yl) amide, 3-chlorodifluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid N- (4'-trifluoromethylbiphenyl-2-yl) -amide and 3-chlorofluoromethyl-1-methyl-1H-pyrazole -4- carboxylic acid N- (4'-trifluoromethylbiphenyl-2-yl) -amide.

9. A composition for controlling harmful fungi, comprising a fungicidal amount of at least one compound of the formula I according to any one of claims 1 to 8 and at least one inert additive.

10. A method for controlling phytopathogenic harmful fungi, characterized in that the harmful fungi, their habitat and / or to be protected against PiIz- infestation materials, plants, the soil or seeds with a fungicidally effective amount of at least one compound of formula I according to one of claims 1 to 8 treated.

11. Use of the compounds I according to any one of claims 1 to 8 for the control of phytopathogenic harmful fungi.

12. Seed containing at least one compound of formula I according to any one of claims 1 to 8 in an amount of 1 to 1000 g per 100 kg of seed.