DE10122097A1 - Pyrazolylbiphenylcarboxamide - Google Patents

Abstract

The invention relates to novel pyrazolyl biphenyl carboxamides of formula (I) wherein R1, R2, X, m, Y and n have the designated meaning as cited in the description. The invention also relates to other methods for producing said materials and the use thereof for controlling undesired microorganisms, in addition to novel intermediate products and the production thereof.

Description

The present invention relates to new pyrazolylbiphenylcarboxamides, several Process for their preparation and their use for combating imm wanted microorganisms.

It has already become known that numerous carboxanilides are fungicidal possess (see WO 93/11 117, EP-A 0 545 099, EP-A 0 589 301, WO 99/09013, DE 198 40 322). This allows 1,3-dimethyl-5-fluoropyrazole-4-carbon acid (2-cyclohexyl) anilide, 1,3-dimethylpyrazole-4-carboxylic acid (2-phenyl) anilide and 1,3-dimethyl-pyrazole-4-carboxylic acid- [2- (2-fluorophenyl)] anilide for combating of mushrooms. The effectiveness of these substances is good, but leaves at low In some cases, application rates leave something to be desired.

New pyrazolylbiphenylcarboxamides of the formula (I)

in which
R ^{1 represents} hydrogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, benzyl or pyridyl methyl,
R ^{2 represents} hydrogen or C ₁ -C ₆ alkyl,
X for halogen, nitro, cyano, hydroxy, carboxyl, C ₁ -C ₈ alkyl, C ₁ -C ₆ halo alkyl having 1 to 5 halogen atoms, C ₁ -C ₈ alkoxy, C ₁ -C ₆ haloalkoxy 1 to 5 halogen atoms, C ₁ -C ₈ alkylthio, C ₁ -C ₆ haloalkylthio with 1 to 5 halogen atoms, C ₂ -C ₈ alkenyloxy, C ₂ -C ₈ alkynyloxy, C ₃ -C ₈ cycloalkyl, C ₁ -C ₈ alkoxycarbonyl or represents -C (R ² ) = N-OR ¹ ,
m represents integers from 0 to 3, where X represents identical or different radicals if m represents 2 or 3,
Y for halogen, nitro, cyano, hydroxy, carboxyl, C ₁ -C ₈ alkyl, C ₁ -C ₆ halo alkyl having 1 to 5 halogen atoms, C ₁ -C ₈ alkoxy, C ₁ -C ₆ haloalkoxy 1 to 5 halogen atoms, C ₁ -C ₈ alkylthio, C ₁ -C ₆ haloalkylthio with 1 to 5 halogen atoms, C ₂ -C ₈ alkenyloxy, C ₂ -C ₈ alkynyloxy, C ₃ -C ₈ cycloalkyl, C ₁ -C ₈ alkoxycarbonyl or C ₁ -C ₆ alkoximino-C ₁ -C ₆ alkyl and
n stands for integers from 0 to 4, where Y stands for identical or different radicals if n stands for 2, 3 or 4,
found.

Furthermore, it was found that pyrazolylbiphenylcarboxamides of the formula (I) can be obtained by

• a) carboxylic acid derivatives of the formula (II)
  in which
  G represents halogen, hydroxy or C ₁ -C ₆ alkoxy,
  with aniline derivatives of the formula (III)
  in which
  R ¹ , R ² , X, m, Y and n have the meanings given above,
  if appropriate in the presence of a catalyst, if appropriate in the presence of an acid binder and if appropriate in the presence of a diluent,
  or
• b) carboxamide derivatives of the formula (IV)
  in which
  X and m have the meanings given above,
  with boronic acid derivatives of the formula (V)
  in which
  R ¹ , R ² , Y and n have the meanings given above and
  G ¹ and G ² each represent hydrogen or together represent tetramethylethylene,
  if appropriate in the presence of a catalyst, if appropriate in the presence of an acid binder and if appropriate in the presence of a diluent,
  or
• c) carboxamide-boronic acid derivatives of the formula (VI)
  in which
  X and m have the meanings given above and
  G ¹ and G ² each represent hydrogen or together represent tetramethylethylene,
  with phenyloxime derivatives of the formula (VII)
  in which
  R ¹ , R ² , Y and n have the meanings given above,
  if appropriate in the presence of a catalyst, if appropriate in the presence of an acid binder and if appropriate in the presence of a diluent,
  or
• d) biphenylacyl derivatives of the formula (VIII)
  in which
  R ² , X, m, Y and n have the meanings given above and
  with alkoxylamines of the formula (IX)
  R ¹ -O-NH ₂ × HCl (IX)
  in which R ^{1 has} the meanings given above,
  if appropriate in the presence of an acid binder and if appropriate in the presence of a diluent,
  or
• e) hydroxylamine derivatives of the formula (Ia)
  in which
  R ² , X, m, Y and n have the meanings given above,
  with compounds of the formula (X)
  R ³ -E (X)
  in which
  R ^{3 represents} C ₁ -C ₆ alkyl and
  E represents chlorine, bromine, iodine, methanesulfonyl or p-toluenesulfonyl,
  or
  R ³ and E together represent (di-C ₁ -C ₆ alkyl) sulfate,
  if appropriate in the presence of an acid binder and if appropriate in the presence of a diluent,
  or
• f) carboxamide derivatives of the formula (IV)
  in which
  X and m have the meanings given above,
  with phenyloxime derivatives of the formula (VII)
  in which
  R ¹ , R ² , Y and n have the meanings given above,
  in the presence of a palladium or platinum catalyst, in the presence of 4,4,4 ', 4', 5,5,5 ', 5'-octamethyl-2,2'-bis-1,3,2-dioxaborolane, if appropriate in the presence of an acid binder and if appropriate in the presence of a diluent.

Finally, it was found that the new pyrazolylbiphenylcarboxamides Formula (I) have very good microbicidal properties and for combating imm desired microorganisms both in crop protection and in material protection are usable.

Surprisingly, the pyrazolylbiphenylcarboxamides according to the invention show of the formula (I) a much better fungicidal activity than the constitutional most similar, previously known active ingredients with the same direction of action.

Formula (I) provides a general definition of the pyrazolylbiphenylcarboxamides according to the invention.
R ¹ preferably represents hydrogen, C ₁ -C ₄ alkyl, C ₁ -C ₂ haloalkyl having 1 to 5 fluorine, chlorine and / or bromine atoms, benzyl or pyridylmethyl.
R ² preferably represents hydrogen or C ₁ -C ₄ alkyl.
X preferably represents fluorine, chlorine, bromine, nitro, cyano, hydroxy, carboxyl, C ₁ -C ₆ alkyl, C ₁ -C ₂ haloalkyl with 1 to 5 fluorine, chlorine and / or bromine atoms, C ₁ - C ₆ alkoxy, C ₁ -C ₂ haloalkoxy with 1 to 5 fluorine, chlorine and / or bromine atoms, C ₁ -C ₆ alkylthio, C ₁ -C ₂ haloalkylthio with 1 to 5 fluorine, chlorine and / or bromine atoms, C ₂ -C ₆ alkenyloxy, C ₂ -C ₆ alkynyloxy, C ₃ -C ₇ cycloalkyl, C ₁ -C ₄ alkoxycarbonyl or for -C (R ² ) = N-OR ¹ .
m preferably represents integers from 0 to 3, where X represents identical or different radicals if m represents 2 or 3.
Y preferably represents fluorine, chlorine, bromine, nitro, cyano, hydroxyl, carboxyl, C ₁ -C ₆ alkyl, C ₁ -C ₂ haloalkyl with 1 to 5 fluorine, chlorine and / or bromine atoms, C ₁ - C ₆ alkoxy, C ₁ -C ₂ haloalkoxy with 1 to 5 fluorine, chlorine and / or bromine atoms, C ₁ -C ₆ alkylthio, C ₁ -C ₂ haloalkylthio with 1 to 5 fluorine, chlorine and / or bromine atoms, C ₂ -C ₆ alkenyloxy, C ₂ -C ₆ alkynyloxy, C ₃ -C ₇ cycloalkyl, C ₁ -C ₄ alkoxycarbonyl or C ₁ -C ₄ alkoximino-C ₁ -C ₄ - alkyl.
n is preferably an integer from 0 to 3, where Y is the same or different radicals if n is 2 or 3.
R ¹ particularly preferably represents hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, 2-chloroethyl, benzyl, 2-pyridylethyl, 3-pyridylmethyl or 4-pyridylmethyl.
R ² particularly preferably represents hydrogen, methyl, ethyl, n-propyl, i-propyl or n-butyl.
X particularly preferably represents fluorine, chlorine, bromine, nitro, cyano, hydroxy, carboxyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, i-butyl, tert-butyl, trichloromethyl, trifluoromethyl , difluoromethyl, Difluorchlor methyl, methoxy, ethoxy, difluoromethoxy, trifluoromethoxy, methylthio, trifluoromethylthio, difluorochloromethylthio, allyloxy, propargyloxy, cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, methoxycarbonyl, ethoxycarbonyl or -C (R ²⁾ = N-oR. ¹
m particularly preferably represents integers from 0 to 2, where X represents the same or different radicals if m represents 2.
Y particularly preferably represents fluorine, chlorine, bromine, nitro, cyano, hydroxy, carboxyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, i-butyl, tert-butyl, trichloromethyl, trifluoromethyl , Difluoromethyl, difluorochloromethyl, methoxy, ethoxy, difluoromethoxy, trifluoromethoxy, methylthio, trifluoromethylthio, difluorochloromethylthio, allyloxy, propargyloxy, cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, methoxycarbonyl, methiminomethylcarbonyl.
n particularly preferably represents integers from 0 to 2, where Y represents identical or different radicals if n represents 2.

Compounds of the formula (Ib) are also preferred

in which
R ¹ , R ² , X, m, Y and n have the meanings given above.

Compounds of the formula (Ib) in which R ¹ , R ² , X, m, Y and n have the meanings given above as preferred or particularly preferred are particularly preferred.

Compounds of the formula (Ic) are also preferred

in which
R ¹ , R ² , X, m, Y and n have the meanings given above.

Particularly preferred are compounds of the formula (Ic) in which R ¹ , R ² , X, m, Y and n have the meanings given above as preferred or particularly preferred.

Compounds of the formula (Id) are also preferred

in which
R ¹ , R ² , X, m, Y and n have the meanings given above.

Particularly preferred are compounds of the formula (Id) in which R ¹ , R ² , X, m, Y and n have the meanings given above as preferred or particularly preferred.

Preferred or particularly preferred are compounds which are preferred under or particularly preferred substituents.

Saturated or unsaturated hydrocarbon radicals such as alkyl or alkenyl can also in connection with heteroatoms such as e.g. B. in alkoxy, where possible, each straight chain or branched.

Optionally substituted radicals can be mono- or polysubstituted, in the case of multiple substitutions, the substituents are the same or different can. Several residues with the same indices as, for example, m residues X for m <1, can be the same or different.

Halogen-substituted radicals, such as. B. haloalkyl, are simple or halogenated several times. With multiple halogenation, the halogen atoms be the same or different. Halogen stands for fluorine, chlorine, bromine and iodine, especially for fluorine, chlorine and bromine.

The general or priority areas listed above However, definitions or explanations can also be made among themselves, i.e. between the respective areas and preferred areas can be combined as desired. they seem for the end products as well as for the preliminary and intermediate products accordingly.

The definitions mentioned can be combined with one another in any way become. In addition, individual definitions can also be omitted.  

If 1,3-dimethyl-5-fluoropyrazole-4-carboxylic acid chloride and 2- (4-meth oximinomethylphenyl) aniline are used as starting materials, the course of process (a) according to the invention can be illustrated by the following formula.

If 1,3-dimethyl-5-fluoropyrazole-4-carboxylic acid (2-bromo) anilide and (4-methoximinomethyl) phenylboronic acid are used as starting materials and a catalyst, process (b) according to the invention can be carried out by the following Formula scheme can be illustrated.

If 2 - [(1,3-dimethyl-5-fluoropyrazol-4-yl) carbonylamino] phenylboronic acid and 1-bromo-2-methoximinomethylbenzene are used as starting materials and a catalyst, the course of the process according to the invention ( c) are illustrated by the following formula scheme.

If 1,3-dimethyl-5-fluoropyrazole-4-carboxylic acid [2- (4-acetyl-phenyl) -4-fluoro] anilide and methoxamine hydrochloride are used as starting materials, the course of process (d) according to the invention can be determined by The following formula scheme can be illustrated.

If 1,3-dimethyl-5-fluoropyrazole-4-carboxylic acid [2- (4-hydroximino ethyl) phenyl] anilide and methyl bromide are used as starting materials, the course of process (e) according to the invention can be illustrated by the following formula become light.

If 1,3-dimethyl-5-fluoropyrazole-4-carboxylic acid (2-bromo) anilide and 1-bromo-4-methoximinomethyl-benzene are used as starting materials, and a catalyst and 4,4,4 ', 4', 5 , 5,5 ', 5'-octamethyl-2,2'-bis-1,3,2-dioxaborolane, the course of process (f) according to the invention can be illustrated by the following formula.

Explanation of the processes and intermediates

The starting materials when carrying out process (a) according to the invention The carboxylic acid derivatives required are generally defined by the formula (II). In this formula represents G preferably chlorine, bromine, hydroxy, methoxy or Ethoxy, particularly preferred for chlorine, hydroxy or methoxy.

The carboxylic acid derivatives of the formula (II) are known or can be reduced produce known processes (cf. WO 93/11 117, EP-A 0 545 099, EP-A 0 589 301 and EP-A 0 589 313).

Formula (III) provides a general definition of the aniline derivatives required as reaction components when carrying out process (a) according to the invention. In this formula, R ¹ , R ² , X, m, Y and n preferably have those meanings which have already been mentioned in connection with the description of the substances of the formula (I) according to the invention, or are particularly preferred for these radicals or these indices ,

The aniline derivatives of the formula (III) are new. They partially subside produce known methods (cf. EP-A 0 545 099 and EP-A 0 589 301).

Aniline derivatives of the formula (III) are also obtained by

• a) 2-haloaniline derivatives of the general formula (XI)
  in which
  X and m have the meanings given above and
  Hal stands for halogen,
  with boronic acid derivatives of the formula (V)
  in which
  R ¹ , R ² , Y, n, G ¹ and G ^{2 have} the meanings given above,
  if appropriate in the presence of an acid binder, and if appropriate in the presence of an inert organic diluent, and if appropriate in the presence of a catalyst
  or
• b) aniline boronic acids of the formula (XII)
  in which
  X, m, G ¹ and G ^{2 have} the meanings given above
  with phenyloxime derivatives of the formula (VII)
  in which
  R ¹ , R ² , Y and n have the meanings given above,
  if appropriate in the presence of an acid binder, and if appropriate in the presence of an inert organic diluent, and if appropriate in the presence of a catalyst.

The reaction com in carrying out the process (g) according to the invention The 2-haloaniline derivatives required by the formula (XI) are general Are defined. In this formula, X and m preferably have the meanings that already in connection with the description of the substances of the invention Formula (I) is preferred or particularly preferred for these radicals or these indices were called. Hal is preferably fluorine, chlorine or bromine, especially preferred for chlorine or bromine.

The 2-haloaniline derivatives of the formula (XI) are commercially available or can be prepared from the corresponding nitro compounds by reduction.

The aniline boronic acids required as reaction components when carrying out process (h) according to the invention are generally defined by the formula (XII). In this formula, X and m preferably have those meanings which have already been mentioned in connection with the description of the substances of the formula (I) according to the invention or are particularly preferred for these radicals or these indices. G ¹ and G ² are preferably each hydrogen or together tetramethylethylene.

The aniline boronic acids of the formula (XII) are commercially available.

When performing the methods (b) and (f) as out Formula (IV) provides general carboxamide derivatives which are required Are defined. In this formula, X and m are preferably those meaning tions already in connection with the description of the invention Substances of the formula (I) for these radicals are mentioned as preferred or particularly preferred were.

The carboxamide derivatives of the formula (IV) are known or can be reduced produce known processes (cf. WO 91/01311, EP-A 0 371 950).  

Formula (V) provides a general definition of the boronic acid derivatives required as reaction components when carrying out process (b) and process (g) according to the invention. In this formula, R ¹ , R ² , Y and n preferably have those meanings which have already been mentioned in connection with the description of the substances of the formula (I) according to the invention or are particularly preferred for these radicals or these indices.

The boronic acid derivatives of the formula (V) are new and can be prepared by

• a) phenylboronic acids of the formula (XIII)
  in which
  R ² , Y, n, G ¹ and G ^{2 have} the meanings given above,
  with alkoxamines of the formula (IX)
  RO-NH ₂ × HCl (IX)
  in which
  R ^{1 has} the meanings given above,
  if appropriate in the presence of an acid binder, and if appropriate in the presence of an inert organic diluent, and if appropriate in the presence of a catalyst.

Formula (XIII) provides a general definition of the phenylboronic acids required as reaction components in carrying out process (h) according to the invention. In this formula, R ² , Y and n preferably have those meanings which have already been mentioned in connection with the description of the substances of the formula (I) according to the invention or have been mentioned particularly preferably for these radicals or these indices. G ¹ and G ² each preferably represent hydrogen or together represent tetramethylethylene.

The phenylboronic acids of the formula (XIII) are commercially available.

Formula (VI) provides a general definition of the carboxamide-boronic acid derivatives required as reaction components when carrying out process (c) according to the invention. In this formula, X and m preferably represent those meanings which have already been mentioned as preferred or particularly preferred in connection with the description of the substances of the formula (I) according to the invention for these radicals. G ¹ and G ² each preferably represent hydrogen or together represent tetramethylethylene.

The carboxamide-boronic acid derivatives of the formula (VI) are new. They can be made by

• a) carboxylic acid derivatives of the formula (II)
  in which
  G has the meanings given above,
  with aniline boronic acids of the formula (XII)
  in which
  X, m, G ¹ and G ^{2 have} the meanings given above
  if appropriate in the presence of an acid binder, and if appropriate in the presence of an inert organic diluent, and if appropriate in the presence of a catalyst.

Formula (VII) provides a general definition of the phenyloxime derivatives required as reaction components when carrying out processes (c), (f) and (h) according to the invention. In this formula, R ¹ , R ² , Y and n preferably have those meanings which have already been mentioned as preferred or particularly preferred for these radicals in connection with the description of the substances of the formula (I) according to the invention.

The phenyloxime derivatives of the formula (VII) are known or can be reduced produce known methods (cf. Synth. Commun. 2000, 30, 665-669, Synth. Commun. 1999, 29, 1697-1701).

Formula (VIII) provides a general definition of the biphenylacyl derivatives required as starting materials when carrying out process (d) according to the invention. In this formula, R ² , X, m, Y and n have the meanings which have already been mentioned as preferred or particularly preferred for these radicals in connection with the description of the substances of the formula (I) according to the invention.

The biphenylacyl derivatives of the formula (VIII) are new. They can be made by

• a) carboxylic acid derivatives of the formula (II)
  in which
  G has the meanings given above,
  with 2-benzaldehyde aniline derivatives of the formula (XIV)
  in which
  R ² , X, m, Y and n have the meanings given above,
  optionally in the presence of an acid binder and optionally in the presence of an inert organic diluent.

Formula (XIV) provides a general definition of the 2-benzaldehyde aniline derivatives required as reaction components when carrying out process (k) according to the invention. In this formula, R ² , X, m, Y and n preferably have those meanings which have already been mentioned as preferred or particularly preferred for these radicals in connection with the description of the substances of the formula (I) according to the invention.

The 2-benzaldehyde aniline derivatives of the formula (XIV) are new. They can be made by

• a) aniline derivatives of the formula (XI)
  in which
  X and m have the meanings given above and
  Hal stands for halogen,
  with phenylboronic acid derivatives of the formula (XIII)
  in which
  R ² , Y, n, G ¹ and G ^{2 have} the meanings given above,
  optionally in the presence of an acid binder and optionally in the presence of an inert organic diluent.

Formula (IX) provides a general definition of the alkoxamines required as reaction components when carrying out process (d) according to the invention and process (i). In this formula, R ¹ preferably has those meanings which have already been mentioned in connection with the description of the substances of the formula (I) according to the invention or have been particularly preferred for this radical. The hydrochlorides specified in the description are preferably used. However, the free alkoxamines can also be used in the process according to the invention.

The alkoxamines of the formula (IX) are commercially available.

Formula (Ia) provides a general definition of the hydroxylamine derivatives required as starting materials when carrying out process (e) according to the invention. In this formula, R ² , X, m, Y and n preferably have those meanings which have already been mentioned as preferred or particularly preferred for these radicals in connection with the description of the substances of the formula (I) according to the invention.

The hydroxylamine derivatives of the formula (I-a) according to the invention are new. You leave according to one of the processes (a), (b), (c) described above, Manufacture (d) or (f).

Formula (X) provides a general definition of the compounds required as reaction components when carrying out process (e) according to the invention. In this formula, R ³ preferably represents C ₁ -C ₄ alkyl, particularly preferably methyl, ethyl, n-propyl, i-propyl or n-butyl. E preferably represents chlorine, bromine, iodine, methanesulfonyl or p-toluenesulfonyl. E particularly preferably represents chlorine or bromine.

The compounds of formula (X) are commercially available.

The acid binders used in carrying out the process according to the invention ren (a), (b), (c), (d), (e) and (f) each have all the usual anorga for such reactions niche and organic bases. Soil is preferably used alkali or alkali metal hydroxides, such as sodium hydroxide, calcium hydroxide, Potassium hydroxide, or ammonium hydroxide, alkali metal carbonates, such as Sodium carbonate, potassium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate, alkali or alkaline earth metal acetates such as sodium acetate, potassium acetate, Calcium acetate, as well as tertiary amines, such as trimethylamine, triethylamine, tributyl amine, N, N-dimethylaniline, pyridine, N-methylpiperidine, N, N-dimethylaminopyridine, Diazabicyclooctane (DABCO), diazabicyclonones (DBN) or diazabicycloundecene (DBU). However, it is also possible to work without an additional acid binder, or to use the amine component in excess so that it is simultaneously acts as an acid binder.

Suitable diluents for carrying out the Ver according to the invention drive (a), (b), (c), (d), (e) and (f) all usual inert organic solvents tien in question. Halogenated aliphas may preferably be used tables, alicyclic or aromatic hydrocarbons, such as petroleum ether, hexane, Heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin; chlorine benzene, 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-diethoxy ethane 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; ester  such as methyl acetate or ethyl acetate, sulfoxides, such as Dimethyl sulfoxide or sulfones such as sulfolane.

The reaction temperatures can be carried out when carrying out the inventive Processes (a), (b), (c), (d), (e) and (f) each vary over a wide range become. Generally one works at temperatures between 0 ° C and 140 ° C, preferably between 10 ° C and 120 ° C.

When carrying out processes (a), (b), (c), (d), (e) and (f) one generally works under atmospheric pressure. But it is also possible Lich to work under increased or reduced pressure.

When carrying out process (a) according to the invention, the starting point is 1 mol Acid halide of formula (II) in general 1 mol or an excess Aniline derivative of the formula (III) and 1 to 3 mol of acid binder. It is however, it is also possible to incorporate the reaction components in other ratios put. The processing takes place according to usual methods. Generally done the orga in such a way that the reaction mixture is mixed with water separated phase and concentrated after drying under reduced pressure. The remaining residue can optionally by conventional methods such as Chromatography or recrystallization of any remaining Verun cleaning can be exempted.

When carrying out process (b) according to the invention, the starting point is 1 mol Carboxamide of formula (IV) in general 1 mol or an excess Boronic acid derivative of the formula (V) and 1 to 5 mol of acid binder. It is however, it is also possible to incorporate the reaction components in other ratios put. The processing takes place according to usual methods. Generally done one in such a way that the reaction mixture is mixed with water, the Nieder blow separates and dries. The remaining residue can if necessary  usual methods, such as chromatography or recrystallization, from possibly still existing impurities are freed.

When carrying out process (c) according to the invention, the starting point is 1 mol Carboxamide-boronic acid derivative of the formula (VI) in general 1 mole or else an excess of phenyloxime derivative of the formula (VII) and 1 to 10 mol Acid binder and 0.5 to 5 mole percent of a catalyst. However, it is also possible to use the reaction components in other ratios. The on work is done according to usual methods. In general, one proceeds in the Way, that the reaction mixture is mixed with water, the precipitate separates and dries. The remaining residue can if necessary usual methods, such as chromatography or recrystallization, from possibly still existing impurities are freed.

When carrying out process (d) according to the invention, the starting point is 1 mol Biphenylacyl derivative of the formula (VIII) in general 1 mol or an excess shot of alkoxamine of formula (IX) and 1 to 5 moles of acid binder. It However, it is also possible to use the reaction components in other ratios put. The processing takes place according to usual methods. Generally done one in such a way that the reaction mixture is mixed with water, the Nieder separated, washed with water and diisopropyl ether and then dried. The remaining residue can optionally by conventional methods such as Chromatography or recrystallization of any remaining Verun cleaning can be exempted.

When carrying out process (e) according to the invention, the starting point is 1 mol Hydroxylamine derivative of the formula (I-a) in general 1 mol or an excess a shot of reagent of formula (X) and 1 to 5 moles of acid binder. It is however, it is also possible to incorporate the reaction components in other ratios put. The processing takes place according to usual methods. Generally done by adding water to the reaction mixture  Precipitate separates and dries. The remaining residue can if necessary usual methods, such as chromatography or recrystallization, from possibly still existing impurities are freed.

When carrying out process (f) according to the invention, the starting point is 1 mol Carboxamide derivative of the formula (IV) in general 1 mol or an excess shot of phenyloxime derivative of formula (VII) and 1 to 5 moles of acid binding medium one, and 1 to 5 moles of a catalyst. However, it is also possible that To use reaction components in other ratios. The workup takes place according to usual methods. In general, one proceeds in such a way that the reaction mixture is mixed with water, the precipitate is separated off and dries. The remaining residue can, if appropriate, be carried out using customary methods, such as chromatography or recrystallization, of any Ver impurities are freed.

The substances according to the invention have a strong microbicidal action and can fight unwanted microorganisms, such as fungi and Bacteria can be used in crop protection and material protection.

Fungicides can be used to control Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Use Deuteromycetes.

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

Some pathogens of fungal and bacterial diseases that fall under the generic names listed above may be mentioned as examples, but not by way of limitation:
Xanthomonas species, such as, for example, Xanthomonas campestris pv. Oryzae;
Pseudomonas species, such as, for example, Pseudomonas syringae pv. Lachrymans;
Erwinia species, such as, for example, Erwinia amylovora;
Pythium species, such as, for example, Pythium ultimum;
Phytophthora species, such as, for example, Phytophthora infestans;
Pseudoperonospora species, such as, for example, Pseudoperonospora humuli or Pseudoperonospora cubensis;
Plasmopara species, such as, for example, Plasmopara viticola;
Bremia species, such as, for example, Bremia lactucae;
Peronospora species, such as, for example, Peronospora pisi or P. brassicae;
Erysiphe species, such as, for example, Erysiphe graminis;
Sphaerotheca species, such as, for example, Sphaerotheca fuliginea;
Podosphaera species, such as, for example, Podosphaera leucotricha;
Venturia species, such as, for example, Venturia inaequalis;
Pyrenophora species, such as, for example, Pyrenophora teres or P. graminea (conidial form: Drechslera, Syn: Helminthosporium);
Cochliobolus species, such as, for example, Cochliobolus sativus (conidial form: Drechslera, Syn: Helminthosporium);
Uromyces species, such as, for example, Uromyces appendiculatus;
Puccinia species, such as, for example, Puccinia recondita;
Sclerotinia species, such as, for example, Sclerotinia sclerotiorum;
Tilletia species, such as, for example, Tilletia caries;
Ustilago species, such as, for example, Ustilago nuda or Ustilago avenae;
Pellicularia species, such as, for example, Pellicularia sasakii;
Pyricularia species, such as, for example, Pyricularia oryzae;
Fusarium species, such as, for example, Fusarium culmorum;
Botrytis species, such as, for example, Botrytis cinerea;
Septoria species, such as, for example, Septoria nodorum;
Leptosphaeria species, such as, for example, Leptosphaeria nodorum;
Cercospora species, such as, for example, Cercospora canescens;
Alternaria species, such as, for example, Alternaria brassicae;
Pseudocercosporella species, such as, for example, Pseudocercosporella herpotrichoides.

The good plant tolerance of the active ingredients in the control of the plant necessary concentrations allow treatment of upper earthly parts of plants, planting and seeds, and the soil.

The active compounds according to the invention can be particularly successful Combating diseases in wine, fruit and vegetable growing, such as for example against Venturia, Botrytis, Sclerotinia, Rhizoctonia, Uncinula, Sphaerotheca, Podosphaera, Alternaria and Colletotrichum species. With good he rice diseases such as Pyricularia and Pellicularia species are also combated.

The active compounds according to the invention are also suitable for increasing the harvest yield. They are also less toxic and show good plant ver indolence.

According to the invention, all plants and parts of plants can be treated. Under Plants are understood here as all plants and plant populations desired and undesirable wild plants or crops (including natural cultivated plants). Cultivated plants can be plants that are caused by conventional breeding and optimization methods or by biotechnological and obtained genetic engineering methods or combinations of these methods can be, including the transgenic plants and including by Plant variety rights of protectable or non-protectable plant varieties. Under Plant parts are said to be all above-ground and underground parts and organs of the Plants such as sprout, leaf, flower and root are understood to be exemplary Leaves, needles, stems, stems, flowers, fruiting bodies, fruits and seeds as well Roots, tubers and rhizomes are listed. One of the plant parts also crops and vegetative and generative propagation material, for example wise cuttings, tubers, rhizomes, offshoots and seeds.  

In material protection, the substances according to the invention can be used to protect tech materials against infestation and destruction by undesirable microorganisms use mechanisms.

In the present context, technical materials include non-living ones Understand materials that have been prepared for use in engineering are. For example, technical materials made by the invention Active substances are to be protected against microbial change or destruction, Adhesives, glue, paper and cardboard, textiles, leather, wood, paints and Plastic items, coolants and other materials can be made by micro organisms can be attacked or decomposed. As part of the to be protected Materials are also parts of production plants, such as cooling water cycles, called, impaired by the multiplication of microorganisms can be. In the context of the present invention are as technical mate rialien preferably adhesives, glue, paper and cardboard, leather, wood, paint called medium, cooling lubricants and heat transfer fluids, especially prefers wood.

As microorganisms that break down or change the technical Materials can cause, for example, bacteria, fungi, yeast, algae and called mucus organisms. The ones according to the invention preferably act Active substances against fungi, in particular mold, wood-discolouring and wood zer disruptive fungi (Basidiomycetes) and against mucous organisms and algae.

For example, microorganisms of the following genera may be mentioned:
Alternaria, such as Alternaria tenuis,
Aspergillus, such as Aspergillus niger,
Chaetomium, like Chaetomium globosum,
Coniophora, such as Coniophora puetana,
Lentinus, such as Lentinus tigrinus,
Penicillium, such as Penicillium glaucum,
Polyporus, such as Polyporus versicolor,
Aureobasidium, such as Aureobasidium pullulans,
Sclerophoma, such as Sclerophoma pityophila,
Trichoderma, like Trichoderma viride,
Escherichia, such as Escherichia coli,
Pseudomonas, such as Pseudomonas aeruginosa,
Staphylococcus, such as Staphylococcus aureus.

The active ingredients can depend on their respective physical and / or chemical properties converted into the usual formulations such as solutions, emulsions, suspensions, powders, foams, pastes, Granules, aerosols, very fine encapsulations in polymeric substances and in coating compositions for seeds, as well as ULV cold and warm mist formulations.

These formulations are prepared in a known manner, e.g. B. by mixing of active ingredients with extenders, i.e. liquid solvents, under pressure standing liquefied gases and / or solid carriers, optionally under Use of surface-active agents, i.e. emulsifiers and / or Dispersing agents and / or foaming agents. In case of using Water as an extender can e.g. B. also organic solvents as auxiliary solution means are used. The liquid solvents essentially come in Question: aromatics such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chlorethylenes or Methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, z. B. petroleum fractions, alcohols such as butanol or glycol and their ethers and Esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclo hexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulfoxide, as well as water. With liquefied gaseous extenders or carriers such liquids are meant, which at normal temperature and below Normal pressure are gaseous, e.g. B. aerosol propellants, such as halogenated hydrocarbon substances as well as butane, propane, nitrogen and carbon dioxide. As solid carriers  come into question: z. B. natural rock flour, such as kaolins, clays, talc, Chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic Rock powders such as finely divided silica, aluminum oxide and silicates. As fixed Carriers for granules are possible: z. B. broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic Granules from inorganic and organic flours as well as granules from organic material such as sawdust, coconut shells, corn cobs and tobacco Columnar. Possible emulsifying and / or foam-generating agents are: B. non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, Polyoxyethylene fatty alcohol ether, e.g. B. alkylaryl polyglycol ethers, alkyl sulfonates, Alkyl sulfates, aryl sulfonates and protein hydrolyzates. Come as a dispersant in question: e.g. B. lignin sulfite and methyl cellulose.

Adhesives such as carboxymethyl cellulose, natural, can be used in the formulations and synthetic powdery, granular or latex-shaped polymers are used, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural phos pholipids such as cephalins and lecithins, and synthetic phospholipids. Further Additives can be mineral and vegetable oils.

Dyes such as inorganic pigments, e.g. B. iron oxide, titanium oxide, ferro cyan and organic dyes such as alizarin, azo and metal phthalalo cyanine 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 percent by weight 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 a mixture with known fungicides, bactericides, acaricides, nematicides or insecticides can be used, e.g. B. the spectrum of action to ver broaden or prevent the development of resistance. In many cases you get it  synergistic effects, d. H. the effectiveness of the mixture is greater than the effectiveness the individual components.

The following connections can be considered as mixed partners:

fungicides

Aldimorph, ampropylfos, ampropylfos potassium, andoprim, anilazine, azaconazole, azoxystrobin,
Benalaxyl, benodanil, benomyl, benzamacril, benzamacrylic isobutyl, bialaphos, binapacrylic, biphenyl, bitertanol, blasticidin-S, bromuconazole, bupirimate, buthiobate,
Calcium polysulfide, capsimycin, captafol, captan, carbendazim, carboxin, carvone, quinomethionate (quinomethionate), chlobenthiazone, chlorfenazole, chloroneb, chloropicrin, chlorothalonil, chlozolinate, clozylacon, cufraneb, cymoxanil, cyphodinconol, cypodinconol
Debacarb, dichlorophene, diclobutrazole, diclofluanid, diclomezin, dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomorph, diniconazole, dini conazol-M, dinocap, diphenylamine, dipyrithione, ditalimfos, dorphianzolone, dithianonol, dithianonol
Ediphenphos, Epoxiconazole, Etaconazole, Ethirimol, Etridiazole,
Famoxadone, fenapanil, fenarimol, fenbuconazole, fenfuram, fenitropan, fenpiclonil, fenpropidin, fenpropimorph, fentin acetate, fentin hydroxide, ferbam, ferimzon, fluazinam, flumetover, fluoromid, fluquinconazole, flurprimolol, flusulfazolutol, flusulfazolutol, flusulfazolutol, flusulfosolutol, flusulfazolutol, flusulfazolutol, flusulfazolutol, flusulfazolutol, flusulfazolutol, flusulfazolutol, flusulfazolutol, flusulfazolutol, flusulfazolutol, flusulfazolutol, flusulfazolutol, flusilazolutol, flusilazolutol, flusulfonol, flusilazolutol, flusulfazolutol, flusilazolutol, flusulfazolutol, flusilazolutol, flusulfazolutolol Fosetyl sodium, fthalide, fuberidazole, furalaxyl, furametpyr, furcarbonil, furconazole, furconazole-cis, furmecyclox,
guazatine,
Hexachlorobenzene, hexaconazole, hymexazole,
Imazalil, Imibenconazol, Iminoctadin, Iminoctadinealbesilat, Iminoctadinetriacetat, Iodocarb, Ipconazol, Iprobefos (IBP), Iprodione, Irumamycin, Isoprothiolan, Isovaledione,
Kasugamycin, Kresoxim-methyl, copper preparations, such as: copper hydroxide, copper naphthenate, copper oxychloride, copper sulfate, copper oxide, oxine-copper and Bordeaux mixture,
Mancopper, Mancozeb, Maneb, Meferimzone, Mepanipyrim, Mepronil, Metalaxyl, Metconazol, Methasulfocarb, Metrifuroxam, Metiram, Metomeclam, Metsulfovax, Mildiomycin, Myclobutanil, Myclozolin,
Nickel dimethyldithiocarbamate, nitrothal isopropyl, Nuarimol,
Ofurace, Oxadixyl, Oxamocarb, Oxolinicacid, Oxycarboxim, Oxyfenthiin,
Paclobutrazole, pefurazoate, penconazole, pencycuron, phosdiphen, pimaricin, piperalin, polyoxin, polyoxorim, probenazole, prochloraz, procymidon, propamocarb, propanosine sodium, propiconazole, propineb, pyrazophos, pyrifen, pyifenox, pyrroyilonil
Quinconazole, quintozen (PCNB), quinoxyfen,
Sulfur and sulfur preparations,
Tebuconazole, tecloftalam, tecnazene, Tetcyclacis, tetraconazole, thiabendazole, Thicyofen, Thifluzamide, thiophanate-methyl, thiram, Tioxymid, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol, Triazbutil, triazoxide, Trichlamid, tricyclazole, tridemorph, triflumizole, triforine, triticonazole,
uniconazole
Validamycin A, vinclozolin, viniconazole,
Zarilamid, Zineb, Ziram as well
Dagger G,
OK 8705,
OK 8801,
α- (1,1-dimethylethyl) -β- (2-phenoxyethyl) -1H-1,2,4-triazole-1-ethanol,
α- (2,4-dichlorophenyl) -β-fluoro-β-propyl-1H-1,2,4-triazole-1-ethanol,
α- (2,4-dichlorophenyl) -β-methoxy-α-methyl-1H-1,2,4-triazole-1-ethanol,
α- (5-methyl-1,3-dioxan-5-yl) -β - [[4- (trifluoromethyl) phenyl] methylene] -1H-1,2,4-triazol-1-ethanol,
(5RS, 6RS) -6-hydroxy-2,2,7,7-tetramethyl-5- (1H-1,2,4-triazol-1-yl) -3-octanone,
(E) -α- (methoxyimino) -N-methyl-2-phenoxy-phenylacetamide,
{2-methyl-1 - [[[1- (4-methylphenyl) ethyl] amino] carbonyl] propyl} carbamic acid 1-isopropyl ester,
1- (2,4-dichlorophenyl) -2- (1H-1,2,4-triazol-1-yl) -ethanone-O- (phenylmethyl) oxime,
1- (2-methyl-1-naphthalenyl) -1H-pyrrole-2,5-dione,
1- (3,5-dichlorophenyl) -3- (2-propenyl) -2,5-pyrrolidinedione,
1 - [(diiodomethyl) sulphonyl] -4-methylbenzene,
1 - [[2- (2,4-dichlorophenyl) -1,3-dioxolan-2-yl] methyl] -1H-imidazole,
1 - [[2- (4-chlorophenyl) -3-phenyloxiranyl] methyl] -1H-1,2,4-triazole,
1- [1- [2 - [(2,4-dichlorophenyl) methoxy] phenyl] ethenyl] -1H-imidazole,
1-methyl-5-nonyl-2- (phenylmethyl) -3-pyrrolidinol,
2 ', 6'-dibromo-2-methyl-4'-trifluoromethoxy-4'-trifluoromethyl-1,3-thiazole-5-carboxanilide,
2,2-dichloro-N- [1- (4-chlorophenyl) ethyl] -1-ethyl-3-methyl-cyclopropanecarboxamide,
2,6-dichloro-5- (methylthio) -4-pyrimidinyl thiocyanate,
2,6-dichloro-N- (4-trifluoromethylbenzyl) -benzamide,
2,6-dichloro-N - [[4- (trifluoromethyl) phenyl] methyl] benzamide,
2- (2,3,3-triiodo-2-propenyl) -2H-tetrazole,
2 - [(1-methylethyl) sulphonyl] -5- (trichloromethyl) -1,3,4-thiadiazole,
2 - [[6-Deoxy-4-O- (4-O-methyl-β-D-glycopyranosyl) -α-D-glucopyranosyl] amino] -4- methoxy-1H-pyrrolo [2,3-d] pyrimidine-5-carbonitrile,
2-aminobutane,
2-bromo-2- (bromomethyl) -pentandinitril,
2-chloro-N- (2,3-dihydro-1,1,3-trimethyl-1H-inden-4-yl) -3-pyridine carboxamide,
2-chloro-N- (2,6-dimethylphenyl) -N- (isothiocyanatomethyl) -acetamide,
2-phenylphenol (OPP),
3,4-dichloro-1- [4- (difluoromethoxy) phenyl] -1H-pyrrole-2,5-dione,
3,5-dichloro-N- [cyano [(1-methyl-2-propynyl) -oxy] -methyl] -benzamide,
3- (1,1-dimethylpropyl) -1-oxo-1H-indene-2-carbonitrile,
3- [2- (4-chlorophenyl) -5-ethoxy-3-isoxazolidinyl] -pyridine,
4-chloro-2-cyano-N, N-dimethyl-5- (4-methylphenyl) -1H-imidazol-1-sulfonamide,
4-methyl-tetrazolo [1,5-a] quinazolin-5 (4H) -one,
8- (1,1-dimethylethyl) -N-ethyl-N-propyl-1,4-dioxaspiro [4.5] decane-2-methanamine,
8-hydroxyquinoline sulfate,
9H-xanthene-9-carboxylic acid 2 - [(phenylamino) carbonyl] hydrazide,
bis (1-methylethyl) -3-methyl-4 - [(3-methylbenzoyl) oxy] -2,5-thiophene dicarboxylate,
cis-1- (4-chlorophenyl) -2- (1H-1,2,4-triazol-1-yl) cycloheptanol,
cis-4- [3- [4- (1,1-dimethylpropyl) phenyl-2-methylpropyl] -2,6-dimethylmorpholine hydrochloride,
Ethyl - [(4-chlorophenyl) azo] cyanoacetate,
potassium bicarbonate,
Methantetrathiol sodium salt,
Methyl-1- (2,3-dihydro-2,2-dimethyl-1H-inden-1-yl) -1H-imidazole-5-carboxylate,
Methyl-N- (2,6-dimethylphenyl) -N- (5-isoxazolylcarbonyl) -DL-alaninate,
Methyl N- (chloroacetyl) -N- (2,6-dimethylphenyl) -DL-alaninate,
N- (2,3-dichloro-4-hydroxyphenyl) -1-methyl-cyclohexanecarboxamide.
N- (2,6-dimethylphenyl) -2-methoxy-N- (tetrahydro-2-oxo-3-furanyl) acetamide,
N- (2,6-dimethylphenyl) -2-methoxy-N- (tetrahydro-2-oxo-3-thienyl) acetamide,
N- (2-chloro-4-nitrophenyl) -4-methyl-3-nitro-benzenesulfonamide,
N- (4-Cyclohexylphenyl) -1,4,5,6-tetrahydro-2-pyrimidinamine,
N- (4-hexylphenyl) -1,4,5,6-tetrahydro-2-pyrimidinamine,
N- (5-chloro-2-methylphenyl) -2-methoxy-N- (2-oxo-3-oxazolidinyl) -acetamide,
N- (6-methoxy) -3-pyridinyl-cyclopropanecarboxamide,
N- [2,2,2-trichloro-1 - [(chloroacetyl) -amino] -ethyl] -benzamide,
N- [3-chloro-4,5-bis- (2-propynyloxy) -phenyl] -N'-methoxy-methanimidamid,
N-formyl-N-hydroxy-DL-alanine-sodium salt,
O, O-diethyl [2- (dipropylamino) -2-oxoethyl] -ethylphosphoramidothioat,
O-methyl-S-phenyl-phenylpropylphosphoramidothioate,
S-Methyl-1,2,3-benzothiadiazole-7-carbothioate,
spiro [2H] -1-benzopyran-2,1 '(3'H) -isobenzofuran] -3'-one.

bactericidal

Bronopol, dichlorophene, nitrapyrin, nickel dimethyldithiocarbamate, kasugamycin, Octhilinone, furan carboxylic acid, oxytetracycline, probenazole, streptomycin, Tecloftalam, copper sulfate and other copper preparations.

Insecticides / acaricides / nematicides

Abamectin, Acephat, Acetamiprid, Acrinathrin, Alanycarb, Aldicarb, Aldoxycarb, Alpha-cypermethrin, Alphamethrin, Amitraz, Avermectin, AZ 60541, Azadirachtin, Azamethiphos, Azinphos A, Azinphos M, Azocyclotin,
Bacillus popilliae, Bacillus sphaericus, Bacillus subtilis, Bacillus thuringiensis, Baculoviruses, Beauveria bassiana, Beauveria tenella, Bendiocarb, Benfuracarb, Bensultap, Benzoximate, Betacyfluthrin, Bifenazate, Bifenthrin, Biethanoprofinoxhrin, Bethenomethrofin, Biobanomethrin Butyl pyridaben
Cadusafos, carbaryl, carbofuran, carbophenothion, carbosulfan, cartap, Chloethocarb, chlorethoxyfos, chlorfenapyr, chlorfenvinphos, chlorfluazuron, chlormephos, chlorpyrifos, chlorpyrifos M, Chlovaphorthrin, cis-resmethrin, Cispermethrin, Clocythrin, cloethocarb, clofentezine, cyanophos, Cycloprene, cycloprothrin, cyfluthrin , Cyhalothrin, cyhexatin, cypermethrin, cyromazine,
Deltamethrin, Demeton M, Demeton S, Demeton-S-methyl, Diafenthiuron, Diazinon, Dichlorvos, Diflubenzuron, Dimethoat, Dimethylvinphos, Diofenolan, Disulfoton, Docusat-sodium, Dofenapyn,
Elfusilanate, Emamectin, Empenthrin, Endosulfan, Entomopfthora spp., Esfenvalerate, Ethiofencarb, Ethion, Ethoprophos, Etofenprox, Etoxazole, Etrimphos,
Fenamiphos, Fenazaquin, Fenbutatinoxide, Fenitrothion, Fenothiocarb, Fenoxacrim, Fenoxycarb, Fenpropathrin, Fenpyrad, Fenpyrithrin, Fenpyroximate, Fenvalerate, Fipronil, Fluazinam, Fluazuron, Flubrocythrinate, Flucycloxxuron, Fluutinoxuron, Fluutinoxuron, Fluutinoxuron, Fluutinoxuron, Fluutinoxinone, furathiocarb,
granulosis,
Halofenozide, HCH, Heptenophos, Hexaflumuron, Hexythiazox, Hydroprene,
Imidacloprid, isazophos, isofenphos, isoxathion, ivermectin,
nucleopolyhedroviruses
Lamda-cyhalothrin, Lufenuron,
Malathion, Mecarbam, Metaldehyde, Methamidophos, Metharhician anisopliae, Metharhician flavoviride, Methidathione, Methiocarb, Methomyl, Methoxyfenozide, Metolcarb, Metoxadiazone, Mevinphos, Milbemectin, Monocrotophos,
Naled, Nitenpyram, Nithiazine, Novaluron,
Omethoate, oxamyl, oxydemethone M,
Paecilomyces fumosoroseus, Parathion A, Parathion M, Permethrin, Phenthoat, Phorat, Phosalon, Phosmet, Phosphamidon, Phoxim, Pirimicarb, Pirimiphos A, Pirimiphos M, Profenophos, Promecarb, Propoxur, Prothiophos, Prothoat, Pyromhrhridosine, Pymmethrofinos, Pymmethrofinos , Pyridathione, pyrimidifen, pyriproxifen,
quinalphos,
ribavirin,
Salithion, Sebufos, Silafluofen, Spinosad, Sulfotep, Sulprofos,
Tau-fluvalinate, tebufenozide, tebufenpyrad, Tebupirimiphos, teflubenzuron, tefluthrin, temephos, Temivinphos, terbufos, tetrachlorvinphos, Thetacypermethrin, thiamethoxam, Thiapronil, Thiatriphos, oxalate hydrogen thiocyclam, thiodicarb, thiofanox, thuringiensin, Tralocythrin, tralomethrin, triarathene, Triazamate, triazophos, Triazuron, trichlophenidine, trichlorfon, triflumuron, trimethacarb,
Vamidothion, Vaniliprole, Verticillium lecanii
YI 5302
Zeta-cypermethrin, zolaprofos
(1R-cis) - [5- (phenylmethyl) -3-furanyl] methyl-3 - [(dihydro-2-oxo-3 (2H) - furanylidene) methyl] -2,2-dimethylcyclopropane carboxylate,
(3-phenoxyphenyl) methyl-2,2,3,3-tetramethylcyclopropanecarboxylat,
1 - [(2-chloro-5-thiazolyl) methyl] tetrahydro-3,5-dimethyl-N-nitro-1,3,5-triazine-2 (1H) - imine,
2- (2-chloro-6-fluorophenyl) -4- [4- (1,1-diemthylethyl) phenyl] -4,5-dihydro-oxazol,
2- (acetyloxy) -3-docecyl-1,4-naphthalinidion,
2-chloro-N - [[[4- (1-phenylethoxy) phenyl] amino] carbonyl] -benzamide,
2-chloro-N - [[[4- (2,2-dichloro-1,1-difluoroethoxy) -phenyl] -amino] -carbonyl] -benzamide,
3-methylphenyl propylcarbamate,
4- [4- (4-ethoxyphenyl) -4-methylpentyl] -1-fluoro-2-phenoxy-benzene,
4-chloro-2- (1,1-dimethylethyl) -5 - [[2- (2,6-dimethyl-4-phenoxyphenoxy) ethyl] thio] - 3 (2H) -pyridazinone,
4-chloro-2- (2-chloro-2-methylpropyl) -5 - [(6-iodo-3-pyridinyl) methoxy] -3 (2H) - pyridazinone,
4-chloro-5 [(6-chloro-3-pyridinyl) methoxy] -2- (3,4-dichlorophenyl) -3 (2H) -pyridazinone,
Bacillus thuringiensis strain EG-2348,
Benzoic acid (2-benzoyl-1- (1,1-dimethylethyl) hydrazide,
Butane 2,2-dimethyl-3- (2,4-dichlorophenyl) -2-oxo-1-oxaspiro [4.5] dec-3-en-4-yl ester,
[3 - [(6-chloro-3-pyridinyl) methyl] -2-thiazolidinylidene] -cyanamide,
Dihydro-2- (nitromethylene) -2H-1,3-thiazine-3 (4H) carboxaldehyde,
Ethyl [2 - [[1,6-dihydro-6-oxo-1- (phenylmethyl) -4-pyridazinyl] oxy] ethyl carbamate,
N- (3,4,4-trifluoro-1-oxo-3-butenyl) -glycine,
N- (4-chlorophenyl) -3- [4-difluoromethoxy) phenyl] -4,5-dihydro-4-phenyl-1H-pyrazole-1-carboxamide,
N - [(2-chloro-5-thiazolyl) methyl] -N'-methyl-N "-nitro-guanidine,
N-methyl-N '- (1-methyl-2-propenyl) -1,2-hydrazindicarbothioamid,
N-methyl-N'-2-propenyl-1,2-hydrazindicarbothioamid,
O, O-diethyl [2- (dipropylamino) -2-oxoethyl] -ethylphosphoramidothioat.

A mixture with other known active ingredients, such as herbicides or with Fertilizers and growth regulators are possible.

In addition, the compounds of formula (I) according to the invention also have very good antifungal effects. They have a very broad spectrum of antifungal effects, especially against dermatophytes and sprout fungi, mold and diphasic fungi,
z. B. against Candida species such as Candida albicans, Candida glabrata, Epidermophy ton species such as Epidermophyton floccosum, Aspergillus species such as Aspergillus niger and Aspergillus fumigatus, Trichophyton species such as Trichophyton mentagro phytes, Microsporon canis and Micro audorini.

The list of these mushrooms in no way places a restriction on what can be detected mycotic spectrum, but is only explanatory.

The active substances can be used as such, in the form of their formulations or in the form thereof prepared application forms, such as ready-to-use solutions, suspensions, Spray powder, pastes, soluble powders, dusts and granules are used become. The application is done in the usual way, e.g. B. by casting, Ver spraying, spraying, scattering, dusting, foaming, brushing etc. It is it is also possible to apply the active ingredients using the ultra-low-volume process or inject the drug preparation or the drug itself into the soil. The seeds of the plants can also be treated.

When using the active compounds according to the invention as fungicides, the on wall quantities vary within a wide range depending on the type of application become. When treating plant parts, the application rates are applied Active ingredient generally between 0.1 and 10,000 g / ha, preferably between 10 and 1000 g / ha. In the case of seed treatment, the active compound application rates are generally between 0.001 and 50 g per kilogram of seed, preferably between 0.01 and 10 g per kilogram of seed. When treating the floor the application rates of active ingredient are generally between 0.1 and 10,000 g / ha, preferably between 1 and 5000 g / ha.  

The agents used to protect technical materials contain the active ingredients generally in an amount of 1 to 95%, preferably 10 to 75%.

The application concentrations of the active compounds according to the invention are directed according to the type and the occurrence of the microorganisms to be controlled and according to the composition of the material to be protected. The optimal use quantity can be determined by test series. In general, the Application concentrations in the range of 0.001 to 5 wt .-%, preferably from 0.05 to 1.0 wt .-% based on the material to be protected.

The effectiveness and spectrum of activity of the material according to the invention protection active ingredients to be used or the means to be produced therefrom, conc Contested or more general wording can be increased if necessary further antimicrobial compounds, fungicides, bactericides, herbicides, Insecticides or other active ingredients to enlarge the spectrum of activity or Achieving special effects such as B. added protection against insects be set. These mixtures can have a broader spectrum of activity than the compounds of the invention.

The manufacture and use of the active compounds according to the invention start out the following examples.  

Preparation Examples

example 1

Procedure (a)

A solution of 1.3 g (0.0057 mol) of 2'-amino-1,1'-biphenyl-4-carbaldehyde-O-methyloximine in 20 mL toluene at room temperature with 0.57 g (0.0057 mol) Triethylamine added. This mixture is allowed to stir at room temperature with stirring a solution of 1.0 g (0.0057 mol) of 5-fluoro-1,3-dimethyl-1H-pyrazole-4-carbonyl chloride drop in 5 mL toluene. When the addition is complete, the reaction mixture heated to 50 ° C and further stirred at this temperature for 2 h. To Aufar The reaction mixture is cooled to room temperature, with further processing 25 ml of toluene are added and the mixture is washed with water. The organic phase is removed separates, dried over sodium sulfate, filtered and concentrated under reduced pressure concentrated. The remaining residue is recrystallized from diisopropyl ether. you receives 1.45 g (69.4% of theory) of 5-fluoro-N- {4 '- [(methoxy imino) methyl] -1,1'-biphenyl-2-yl} -1,3-dimethyl-1H-pyrazole-4-carboxamide as color loose crystals with a melting point of 114 to 116 ° C.  

Example 2

Method (b)

A mixture of 0.35 g (0.001 mol) of N- (2-bromo-4,6-difluorophenyl) -5-fluoro-1,3- dimethyl-1H-pyrazole-4-carboxamide, 0.06 g (0.00005 mol) of tetrakis (triphenylphos phin) palladium, 0.32 g (0.0018 mol) of 4 - [(methoxyimino) methyl] phenylboronic acid and 10 mL 1,2-dimethoxyethane is mixed with a solution of 0.5 g (0.0047 mol) of sodium carbonate was added to 3 ml of water. The reaction mixture is then brought to reflux temperature and held there for 15 h. For working up, the reaction mixture is stirred in 200 ml of water. The first The precipitate is filtered off and dried. The remaining residue is chro with cyclohexane: ethyl acetate = 1: 1 as eluent on silica gel matographiert. After concentrating the eluate, 0.20 g (48% of theory) are obtained. an N- {3,5-difluoro-4 '- [(methoxyimino) methyl] -1,1'-biphenyl-2-yl} -5-fluoro-1,3- dimethyl-1H-pyrazole-4-carboxamide in the form of a solid with an enamel point from 164 to 167 ° C.  

Example 3

Procedure (c)

To a mixture of 0.71 g (2 mmol) of 5-fluoro-1,3-dimethyl-N- [2- (4,4,5,5-tetra methyl-1,3,2-dioxaborolan-2-yl ) phenyl] -1H-pyrazole-4-carboxamide, 1.39 g (6 mmol) of 4-bromo-2-fluorobenzaldehyde-O-methyloxime, 0.03 g (0.05 mmol) of PdCl ₂ (dppf) and 40 mL Dimethyl sulfoxide, 1.28 g (12 mmol) sodium carbonate, dissolved in 6 mL water, are added at room temperature. The reaction mixture is stirred at 80 ° C for 15 hours.

For working up, the reaction mixture is stirred in 400 ml of water, the Nieder extracted and dried. The crude product is then on silica gel with cyclohexane: ethyl acetate = 1: 1 as eluent, column chromatography nigt. After concentration, 0.11 g (14% of theory) of 5-fluoro-N- {3'-fluoro- 4 '- [(methoxyimino) methyl] -1,1'-biphenyl-2-yl} -1,3-dimethyl-1H-pyrazol-4-carbox amide as crystals with a melting point of 158 to 161 ° C.  

Example 4

Method (d)

A mixture of 1.0 g (0.0028 mol) of N- (4'-acetyl-1,1'-biphenyl-2-yl) -5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide 0.30 g (0.0036 mol) of O-methylhydroxylamine hydrochloride, 0.30 g (0.0036 mol) of sodium acetate and 6 ml of methanol are stirred at room temperature for 12 h. For working up, the reaction mixture is stirred in water, the precipitate formed is suction filtered, washed with water and then a little diisopropyl ether and dried. 0.91 g (85.4% of theory) of 5-fluoro-N- [4 '- (N-methoxyethanimidoyl) -1,1'-biphenyl-2-yl] -1,3-dimethyl-1H is obtained -pyrazole-4-carboxamide with a melting point of 153 ° C.
¹ H-NMR spectrum (DMSO / TMS): δ = 3.60 ppm.

Manufacture of starting substances

Process (g)

A mixture of 2.9 g (0.017 mol) of 2-bromoaniline, 0.68 g of tetrakis (triphenylphosphine) palladium, 5.5 g (0.031 mol) of 4 - [(methoxyimino) methyl] phenylboronic acid and 40 ml of 1.2 -Dimethoxyethane is mixed at room temperature with a solution of 8.2 g (0.077 mol) of sodium carbonate in 35 ml of water. The reaction mixture is then brought to reflux temperature and boiled for 12 h. To work up is cooled to room temperature and extracted with diethyl ether. The organic phase is separated off and water is added. The organic phase is separated off again, dried over sodium sulfate and finally concentrated under reduced pressure. The remaining residue is chromatographed on silica gel using mobile phase = 3: 1 as the eluent. After concentrating the eluate, 3.8 g (98.8% of theory based on 2-bromoaniline) of 2'-amino-1,1'-biphenyl-4-carbaldehyde-O-methyloxime are obtained in the form of an oil.
¹ H-NMR spectrum (DMSO / TMS): δ = 3.90 (3H) ppm.

Procedure (i)

A mixture of 5.0 g (0.033 mol) of 4-formylphenylboronic acid, 3.4 g (0.041 mol) of O-methylhydroxylamine hydrochloride, 3.4 g (0.041 mol) of sodium acetate, 40 ml of methanol and 10 ml of water are stirred for 12 hours at room temperature , For working up, the reaction mixture is stirred in water, the resulting precipitate is filtered off with suction, washed with water and dried at 50 ° C. in vacuo. 5.56 g (93.1% of theory) of 4 - [(methoxyimino) methyl] phenylboronic acid are obtained as colorless crystals with a melting point of 199 to 200 ° C.

Procedure (j)

To a mixture of 0.39 g (1.5 mmol) of 2- (4,4,5,5-tetramethyl-1,3,2-dioxaboro Lan-2-yl) aniline hydrochloride and 20 mL acetonitrile are 0.55 g (4 mmol) potassium carbonate and 0.30 g (0.0017 mol) of 5-fluoro-1,3-dimethyl-1H-pyrazole-4-carbonylchlo rid added at room temperature. The reaction mixture is 20 h at Raumtem temperature stirred.

For working up, the reaction mixture is stirred in 150 mL water, with vinegar extracted ethyl acetate and dried over sodium sulfate. The organic phase is concentrated under reduced pressure and the solid residue in diisopropyl ether stirred. 0.25 g (46% of theory) of 5-fluoro-1,3-dimethyl-N- [2- (4,4,5,5- tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl] -1H-pyrazol-4-carboxamide in the form of Crystals with a melting point of 100 to 103 ° C.

Following the previously described methods are also those in the table below biphenylcarboxamides of the formula (I) prepared.  

Table 1

The determination of those in the tables and manufacturing examples above specified logP values are carried out in accordance with EEC Directive 79/831 Annex V.A8 HPLC (High Performance Liquid Chromatography) on a phase reversal column (C18). Temperature: 43 ° C.

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

The determination is carried out in the neutral range at pH 7.5 with 0.01 molar aqueous phosphate buffer solution and acetonitrile as eluent; linear gradient from 10% acetonitrile to 90% acetonitrile (marked with ^b in the table).

The calibration is carried out with unbranched alkan-2-ones (with 3 to 16 carbon atoms men) whose logP values are known (determination of the logP values using the Re tention times through linear interpolation between two consecutive alkas nonene).

The lambda max values were determined using the UV spectra from 200 nm to 400 nm the maxima of the chromatographic signals determined.

applications Example A Podosphaera test (apple) / protective

Solvent: 24.5 parts by weight of acetone
24.5 parts by weight of dimethylacetamide
Emulsifier: 1.0 part by weight of alkyl aryl polyglycol ether.

To produce a suitable preparation of active compound, it is mixed 1 part by weight of active ingredient with the stated amounts of solvent and emul gator and dilute the concentrate with water to the desired concentration.

To test for protective effectiveness, young plants are used with the active ingredient preparation sprayed in the specified application rate. After the The plants are sprayed with an aqueous spore suspension of the apple mildew pathogen Podosphaera leucotricha inoculated. The plants are then in the Greenhouse at approx. 23 ° C and a relative humidity of approx. 70% provides.

Evaluation is carried out 10 days after the inoculation. 0% means a we efficiency that corresponds to that of the control, while an efficiency of 100% means that no infection is observed.

In this test, e.g. B. the following compounds of the invention Production examples superior effectiveness compared to the prior art:  

Table A

Podosphaera test (apple) / protective

Example B Sphaerotheca test (cucumber) / protective

Solvent: 24.5 parts by weight of acetone
24.5 parts by weight of dimethylacetamide
Emulsifier: 1.0 part by weight of alkyl aryl polyglycol ether.

To produce a suitable preparation of active compound, it is mixed 1 part by weight of active ingredient with the stated amounts of solvent and emulga tor and dilute the concentrate with water to the desired concentration.

To test for protective effectiveness, young plants are used with the active ingredient preparation sprayed in the specified application rate. After the The plants are sprayed with an aqueous spore suspension from Sphae rotheca fuliginea inoculated. The plants are then at about 23 ° C and a rela 70% humidity in the greenhouse.

Evaluation is carried out 10 days after the inoculation. 0% means a Efficiency that corresponds to that of the control, while an efficiency 100% means that no infection is observed.

In this test, e.g. B. the following compounds of the invention Production examples superior effectiveness compared to the prior art:  

Table B

Sphaerotheca test (cucumber) / protective

Example C Venturia test (apple) / protective

Solvent: 24.5 parts by weight of acetone
24.5 parts by weight of dimethylacetamide
Emulsifier: 1.0 part by weight of alkyl aryl polyglycol ether.

To produce a suitable preparation of active compound, it is mixed 1 part by weight of active ingredient with the stated amounts of solvent and emul gator and dilute the concentrate with water to the desired concentration.

To test for protective effectiveness, young plants are used with the active ingredient preparation sprayed in the specified application rate. After the The plants are sprayed with an aqueous conidia suspension of Apple scab pathogen Venturia inaequalis and then remain for 1 day at approx. 20 ° C and 100% relative humidity in an incubation cabin.

The plants are then grown in a greenhouse at approx. 21 ° C and relative air humidity of approx. 90%.

Evaluation is carried out 12 days after the inoculation. 0% means a Efficiency that corresponds to that of the control, while an efficiency 100% means that no infection is observed.

In this test, e.g. B. the following compounds of the invention Production examples superior effectiveness compared to the prior art:  

Table C.

Venturia test (apple) / protective

Example D Puccinia test (wheat) / protective

Solvent: 25 parts by weight of N, N-dimethylacetamide
Emulsifier: 0.6 part by weight of alkylaryl polyglycol ether.

To produce a suitable preparation of active compound, 1 weight is mixed some active ingredient with the specified amounts of solvent and emulsifier and dilute the concentrate with water to the desired concentration.

To test for protective effectiveness, young plants are used with the active ingredient preparation sprayed in the specified application rate. After the The plants are sprayed with a conidia suspension of Puccinia recon dita sprayed. The plants remain at 20 ° C. and 100% relative air for 48 hours humidity in an incubation cabin.

The plants are then grown in a greenhouse at a temperature of approximately 20 ° C and a relative humidity of 80% set up to the development of Favor rust pustules.

Evaluation is carried out 10 days after the inoculation. 0% means a Efficiency that corresponds to that of the control, while an efficiency 100% means that no infection is observed.

In this test, e.g. B. the following compounds of the invention Production examples superior effectiveness compared to the prior art:  

Table D

Puccinia test (wheat) / protective

Example E Alternaria test (tomato) / protective

Solvent: 49 parts by weight of N, N-dimethylformamide
Emulsifier: 1 part by weight of alkylaryl polyglycol ether.

To produce a suitable preparation of active compound, it is mixed 1 part by weight of active ingredient with the stated amounts of solvent and emulsifier and dilute the concentrate with water to the desired concentration.

To test for protective effectiveness, young tomato plants are sprayed with the Active ingredient preparation in the specified application rate. 1 day after treatment the plants are inoculated with a spore suspension of Alternaria solani and are then 24 h at 100% rel. Humidity and 20 ° C. Then the plants stand at 96% rel. Humidity and a temperature of 20 ° C.

Evaluation is carried out 7 days after the inoculation. 0% means a Efficiency that corresponds to that of the control, while an efficiency 100% means that no infection is observed.

In this test, e.g. B. the following compounds of the invention Production examples superior effectiveness compared to the prior art:  

Table E

Alternaria test (tomato) / protective

Example F Inhibition test on giant colonies of Basidiomycetes

From colonies of Gloeophyllum trabeum, Coniophora puteana, Poria placenta, Lentinus tigrinus and Coriolus versicolor were cut out and put on mycelium pieces incubated with a malt extract-peptone-containing agar medium at 26 ° C. The Inhibition of hyphal growth on nutrient-containing nutrient media was carried out with the Length growth compared to nutrient medium without the addition of active ingredient and as percentage inhibition rated.

In this test, e.g. B. the following compounds of the invention Production examples good effectiveness:  

Table F

Inhibition test on giant colonies of Basidiomycetes

Claims (21)

1. pyrazolylbiphenylcarboxamides of the formula (I)
in which
R ^{1 represents} hydrogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ haloalkyl, benzyl or pyridylmethyl,
R ^{2 represents} hydrogen or C ₁ -C ₆ alkyl,
X for halogen, nitro, cyano, hydroxy, carboxyl, C ₁ -C ₈ alkyl, C ₁ -C ₆ haloalkyl with 1 to 5 halogen atoms, C ₁ -C ₈ alkoxy, C ₁ -C ₆ halo genalkoxy with 1 to 5 halogen atoms, C ₁ -C ₈ alkylthio, C ₁ -C ₆ halo alkylthio with 1 to 5 halogen atoms, C ₂ -C ₈ alkenyloxy, C ₂ -C ₈ alkynyloxy, C ₃ -C ₈ cycloalkyl , C ₁ -C ₈ alkoxycarbonyl or represents -C (R ² ) = N-OR ¹ ,
m stands for integers from 0 to 3, where X stands for identical or different radicals if m stands for 2 or 3,
Y for halogen, nitro, cyano, hydroxy, carboxyl, C ₁ -C ₈ alkyl, C ₁ -C ₆ haloalkyl with 1 to 5 halogen atoms, C ₁ -C ₈ alkoxy, C ₁ -C ₆ halo genalkoxy with 1 to 5 halogen atoms, C ₁ -C ₈ alkylthio, C ₁ -C ₆ haloalkylthio with 1 to 5 halogen atoms, C ₂ -C ₈ alkenyloxy, C ₂ -C ₈ alkynyloxy, C ₃ -C ₈ cycloalkyl, C ₁ -C ₈ alkoxycarbonyl or C ₁ -C ₆ alkoximino-C ₁ -C ₆ alkyl and
n is an integer from 0 to 4, where Y is the same or different radicals when n is 2, 3 or 4. 2. pyrazolylbiphenylcarboxamides of the formula (I) according to claim 1, in which
R ^{1 represents} hydrogen, C ₁ -C ₄ alkyl, C ₁ -C ₂ haloalkyl with 1 to 5 fluorine, chlorine and / or bromine atoms, benzyl or pyridylmethyl,
R ^{2 represents} hydrogen or C ₁ -C ₄ alkyl,
X for fluorine, chlorine, bromine, nitro, cyano, hydroxy, carboxyl, C ₁ -C ₆ alkyl, C ₁ -C ₂ haloalkyl with 1 to 5 fluorine, chlorine and / or bromine atoms, C ₁ -C ₆ -Alkoxy, C ₁ -C ₂ -haloalkoxy with 1 to 5 fluorine, chlorine and / or bromine atoms, C ₁ -C ₆ -alkylthio, C ₁ -C ₂ -halogenal kylthio with 1 to 5 fluorine, chlorine and / or bromine atoms, C ₂ -C ₆ alkynyloxy, C ₂ -C ₆ alkynyloxy, C ₃ -C ₇ cycloalkyl, C ₁ -C ₄ alkoxycarbonyl or represents -C (R ² ) = N-OR ¹ ,
m stands for integers from 0 to 3, where X stands for identical or different radicals if m stands for 2 or 3,
Y for fluorine, chlorine, bromine, nitro, cyano, hydroxy, carboxyl, C ₁ -C ₆ alkyl, C ₁ -C ₂ haloalkyl with 1 to 5 fluorine, chlorine and / or bromine atoms, C ₁ -C ₆ Alkoxy, C ₁ -C ₂ haloalkoxy with 1 to 5 fluorine, chlorine and / or bromine atoms, C ₁ -C ₆ alkylthio, C ₁ -C ₂ halo alkylthio with 1 to 5 fluorine, chlorine and / or bromine atoms, C ₂ -C ₆ alkenyloxy, C ₂ -C ₆ alkynyloxy, C ₃ -C ₇ cycloalkyl, C ₁ -C ₄ alkoxy carbonyl or C ₁ -C ₄ alkoximino-C ₁ -C ₄ - alkyl stands,
n is an integer from 0 to 3, where Y is the same or different radicals when n is 2 or 3. 3. pyrazolylbiphenylcarboxamides of the formula (I) according to claim 1, in which
R ^{1 is} hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, 2-chloroethyl, benzyl, 2-pyridylmethyl, 3-pyridyl methyl or 4- Pyridylmethyl stands,
R ^{2 represents} hydrogen, methyl, ethyl, n-propyl, i-propyl or n-butyl,
X for fluorine, chlorine, bromine, nitro, cyano, hydroxy, carboxyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, i-butyl, tert-butyl, trichloromethyl, trifluoromethyl, difluoromethyl, difluorochloromethyl, methoxy, ethoxy, difluoromethoxy, trifluoromethoxy, methylthio, trifluoromethylthio, difluorochloromethylthio, allyloxy, propargyloxy, cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, Methoxycarb onyl, ethoxycarbonyl, or represents -C (R ²⁾ = N-oR ^1,
m stands for integers from 0 to 2, where X stands for identical or different residues if m stands for 2,
Y for fluorine, chlorine, bromine, nitro, cyano, hydroxy, carboxyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, i-butyl, tert-butyl, trichloromethyl, trifluoromethyl, difluoromethyl, Difluorochloromethyl, methoxy, ethoxy, difluoromethoxy, trifluoromethoxy, methylthio, trifluoromethylthio, difluorochloromethylthio, allyloxy, propargyloxy, cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, methoxycarb onyl, ethoxycarbonyl or methoximinomethyl,
n stands for integers from 0 to 2, where Y stands for identical or different residues if n stands for 2. 4. A process for the preparation of pyrazolylbiphenylcarboxamides of the formula (I) according to claim 1, characterized in that

• 1. Carboxylic acid derivatives of the formula (II)
  in which
  G represents halogen, hydroxy or C ₁ -C ₆ alkoxy,
  with aniline derivatives of the formula (III)
  in which
  R ¹ , R ² , X, m, Y and n have the meanings given in claim 1,
  if appropriate in the presence of a catalyst, if appropriate in the presence of an acid binder and if appropriate in the presence of a diluent,
  or
• 2. Carboxamide derivatives of the formula (IV)
  in which
  X and m have the meanings given in claim 1,
  with boronic acid derivatives of the formula (V)
  in which
  R ¹ , R ² , Y and n have the meanings given in claim 1 and
  G ¹ and G ² each represent hydrogen or together represent tetramethyl ethylene,
  if appropriate in the presence of a catalyst, if appropriate in the presence of an acid binder and if appropriate in the presence of a diluent,
  or
• 3. Carboxamide-boronic acid derivatives of the formula (VI)
  in which
  X and m have the meanings given in claim 1 and
  G ¹ and G ² each represent hydrogen or together represent tetramethyl ethylene,
  with phenyloxime derivatives of the formula (VII)
  in which
  R ¹ , R ² , Y and n have the meanings given in Claim 1,
  if appropriate in the presence of a catalyst, if appropriate in the presence of an acid binder and if appropriate in the presence of a diluent,
  or
• 4. Biphenylacyl derivatives of the formula (VIII)
  in which
  R ² , X, m, Y and n have the meanings given in claim 1,
  with alkoxamines of the formula (IX)
  R ¹ -O-NH ₂ × HCl (IX)
  in which R ^{1 has} the meanings given in claim 1,
  if appropriate in the presence of an acid binder and if appropriate in the presence of a diluent,
  or
• 5. Hydroxylamine derivatives of the formula (Ia)
  in which
  R ² , X, m, Y and n have the meanings given in claim 1,
  with compounds of the formula (X)
  R ³ -E (X)
  in which
  R ^{3 represents} C ₁ -C ₆ alkyl and
  E represents chlorine, bromine, iodine, methanesulfonyl or p-toluenesulfonyl,
  or
  R ³ and E together represent (di-C ₁ -C ₆ alkyl) sulfate,
  if appropriate in the presence of an acid binder and if appropriate in the presence of a diluent,
  or
• 6. Carboxamide derivatives of the formula (IV)
  in which
  X and m have the meanings given in claim 1,
  with phenyloxime derivatives of the formula (VII)
  in which
  R ¹ , R ² , Y and n have the meanings given in Claim 1,
  in the presence of a palladium or platinum catalyst and in the presence of 4,4,4 ', 4', 5,5,5 ', 5'-octamethyl-2,2'-bis-1,3,2-dioxaborolane , ge if appropriate in the presence of an acid binder and if appropriate in the presence of a diluent.

5. pyrazolylbiphenylcarboxamides of the formula (Ib)
in which
R ¹ , R ² , X, m, Y and n have the meanings given in claim 1. 6. pyrazolylbiphenylcarboxamides of the formula (Ic)
in which
R ¹ , R ² , X, m, Y and n have the meanings given in claim 1. 7. pyrazolylbiphenylcarboxamides of the formula (Id)
in which
R ¹ , R ² , X, m, Y and n have the meanings given in claim 1. 8. Aniline derivatives of the formula (III)
in which
R ¹ , R ² , X, m, Y and n have the meanings given in claim 1. 9. A process for the preparation of aniline derivatives of the formula (III) according to claim 8, characterized in that

• 1. 2-haloaniline derivatives of the general formula (XI)
  in which
  X and m have the meanings given in claim 1 and
  Hal stands for halogen,
  with boronic acid derivatives of the formula (V)
  in which
  R ¹ , R ² , Y and n have the meanings given in claim 1 and
  G ¹ and G ² each represent hydrogen or together represent tetramethyl ethylene,
  if appropriate in the presence of an acid binder, and if appropriate in the presence of an inert organic diluent, and if appropriate in the presence of a catalyst
  or
• 2. Aniline boronic acids of the formula (XII)
  in which
  X and m have the meanings given in claim 1 and
  G ¹ and G ² each represent hydrogen or together represent tetramethyl ethylene,
  with phenyloxime derivatives of the formula (VII)
  in which
  R ¹ , R ² , Y and n have the meanings given in claim 1,
  if appropriate in the presence of an acid binder, and if appropriate in the presence of an inert organic diluent, and if appropriate in the presence of a catalyst.

10. Boronic acid derivatives of the formula (V)
in which
R ¹ , R ² , Y and n have the meanings given in claim 1 and
G ¹ and G ² each represent hydrogen or together represent tetramethylethylene. 11. A process for the preparation of boronic acid derivatives of the formula (V) according to claim 10, characterized in that

• 1. Phenylboronic acids of the formula (XIII)
  in which
  R ² , Y and n have the meanings given in claim 1 and
  G ¹ and G ² each represent hydrogen or together represent tetramethyl ethylene,
  with alkoxamines of the formula (IX)
  R ¹ -O-NH ₂ × HCl (IX)
  in which
  R ^{1 has} the meanings given in claim 1,
  if appropriate in the presence of an acid binder, and if appropriate in the presence of an inert organic diluent, and if appropriate in the presence of a catalyst.

12. Carboxamide boronic acid derivatives of the formula (VI)
in which
X and m have the meanings given in claim 1 and
G ¹ and G ² each represent hydrogen or together represent tetramethylethylene. 13. A process for the preparation of carboxamide-boronic acid derivatives of the formula (VI) according to claim 12, characterized in that

• 1. Carboxylic acid derivatives of the formula (II)
  in which
  G has the meanings given in claim 1,
  with aniline boronic acids of the formula (XII)
  in which
  X and m have the meanings given in claim 1 and
  G ¹ and G ² each represent hydrogen or together represent tetramethyl ethylene,
  if appropriate in the presence of an acid binder, and if appropriate in the presence of an inert organic diluent, and if appropriate in the presence of a catalyst.

14. Biphenylacyl derivatives of the formula (VIII)
in which
R ² , X, m, Y and n have the meanings given in claim 1. 15. A process for the preparation of biphenylacyl derivatives of the formula (VIII) according to claim 14, characterized in that

• 1. Carboxylic acid derivatives of the formula (II)
  in which
  G has the meanings given in claim 1,
  with 2-benzaldehyde aniline derivatives of the formula (XIV)
  in which
  R ² , X, m, Y and n have the meanings given in claim 1,
  optionally in the presence of an acid binder, and if appropriate in the presence of an inert organic diluent.

16. 2-Benzaldehyde aniline derivatives of the formula (XIV)
in which
R ² , X, m, Y and n have the meanings given in claim 1. 17. A process for the preparation of 2-benzaldehyde aniline derivatives of the formula (XIV) according to claim 16, characterized in that

• 1. Aniline derivatives of the formula (XI)
  in which
  X and m have the meanings given in claim 1 and
  Hal stands for halogen,
  with phenylboronic acid derivatives of the formula (XIII)
  in which
  R ² , Y and n have the meanings given in claim 1 and
  G ¹ and G ² each represent hydrogen or together represent tetramethyl ethylene,
  optionally in the presence of an acid binder, and if appropriate in the presence of an inert organic diluent.

18. Agents for combating undesirable microorganisms, characterized by containing at least one pyrazolylbiphenylcarboxamide Formula (I) according to claim 1 in addition to extenders and / or surfaces active substances. 19. Use of pyrazolylbiphenylcarboxamides of the formula (I) according to Claim 1 to combat unwanted microorganisms. 20. Process for combating undesirable microorganisms, thereby ge indicates that pyrazolylbiphenylcarboxamides of the formula (I) according to Claim 1 to the microorganisms and / or their habitat. 21. Process for the preparation of agents for combating undesirable Microorganisms, characterized in that pyrazolylbiphenyl carboxamides of formula (I) according to claim 1 with extenders and / or surface-active substances mixed.