DE19547633A1 - New hetero-aryl-carboxamide compounds - Google Patents

Abstract

The following are claimed: (A) heteroaryl-carboxamide compounds of formula (I): G = S(O)n, CH2-S(O)n, C(R<3>)=N-O, N=C(R<3>)-Q<1>, N(R<4>)-C(R<3>)=N-O or N=N-C(R<3>)=N-O, in each of which the O or S atom is linked to the CH2 group attached to the heterocycle; or Q<1>-C(R<3>)=N-O or Q<1>-CH2-C(R<3>)=N-O, in each of which the group Z is linked to Q<1>; n = 0-2; Q<1> = O or S; R<3> = H or CN; or is alkyl, alkoxy, alkylthio, alkylamino, dialkylamino or cycloalkyl (all optionally substituted); R<4> = H, OH or CN; or alkyl, alkoxy or cycloalkyl (all optionally substituted); Q = O or S; R<1> = H, alkyl or cycloalkyl; R<2> = alkyl, alkoxy or cycloalkyl; or aryl or heterocyclyl (both optionally substituted); or NR<1>R<2> = an optionally substituted heterocyclic ring; Y = O or S; Z = optionally substituted aryl or heterocyclyl. (B) intermediates of formula (IIa): X = halo; (C) intermediates of formulae (IV) and (V). R<5> = alkyl.

Description

The present invention relates to new heteroarylcarboxamides, a process ren for their preparation and their use as microbicides. The invention be also meets new intermediates and several processes for their manufacture lung.

It has already been known that certain 3-furan carboxamides fungizi have properties (cf. DE-A 20 06 471). The effect of this connection gene is not always satisfactory at low application rates.

There have now been new heteroarylcarboxamides of the formula

in which
G for oxygen or a grouping of the formula

is, in each case the oxygen or sulfur atom is linked to the -CH₂ group bonded to the heterocycle,
or for a grouping of the formula

stands,
where the remainder Z is connected to Q 1,
in which
n represents the numbers 0, 1 or 2,
Q¹ represents oxygen or sulfur,
R³ represents hydrogen, cyano or in each case optionally substituted alkyl, alkoxy, alkylthio, alkylamino, dialkylamino or cycloalkyl, and
R⁴ represents hydrogen, hydroxy, cyano or in each case optionally substituted alkyl, alkoxy or cycloalkyl,
Q represents oxygen or sulfur,
R¹ represents hydrogen, alkyl or cycloalkyl,
R² represents alkyl, alkoxy, cycloalkyl, optionally substituted aryl or optionally substituted heterocyclyl,
or R¹ and R² together with the nitrogen atom to which they are attached form an optionally substituted heterocyclic ring,
Y stands for oxygen or sulfur and
Z stands for optionally substituted aryl or heterocyclyl,
found.

It has also been found that heteroarylcarboxamides of the formula (I) obtained when carboxylic acid halides of the formula

in which
G, Q and Z have the meanings given above and X represents halogen,
with amines of the formula

in which
R¹ and R² have the meanings given above,
if appropriate in the presence of an acid acceptor and if appropriate in the presence of a diluent and if appropriate the resulting amides of the formula

in which
G, Q, R¹, R² and Z have the meanings given above,
with a sulfurization reagent, optionally in the presence of a diluent.

Finally, it was found that the new heteroarylcarboxamides from For mel (I) have very strong microbicidal, in particular fungicidal activity.

Surprisingly, the substances according to the invention are particularly suitable to combat unwanted microorganisms, such as fungi, than the con the most similar in terms of stitution, previously known substances with the same direction of action.

Those substances according to the invention in which C = C double bonds in the are present, optionally in the form of stereoisomers such as  E and Z isomers are obtained. The invention relates to both the E and the Z Isomers and also any mixtures of these isomers.

The heteroarylcarboxamides according to the invention are all of the formula (I) commonly defined.

Unless otherwise defined, alkyl is in the substituent meanings in each case for straight-chain or branched residues. Also alkoxy, alkylthio or alkylamino unless otherwise defined, stand for residues with straight-chain or branched Carbon chains.

Unless otherwise defined, halogen stands for fluorine, chlorine, bromine or iodine as well also for pseudohalogens, such as cyano.

Unless otherwise defined, aryl stands for aromatic, mono- or polycyclic Hydrocarbon rings such as phenyl, naphthyl, anthranyl or phenanthryl.

Unless otherwise defined, heterocyclyl stands for saturated or unsaturated, ge optionally aromatic, ring-shaped radicals in which at least one ring member a heteroatom, d. H. is an atom other than carbon. Contains the If several heteroatoms ring, they can be the same or different. Straight atoms are preferably oxygen, nitrogen or sulfur. Contains one ring oxygen atoms, they are not adjacent. If necessary, form the ring-shaped compounds with other carbocyclic or heterocyclic, fused or bridged rings together form a polycyclic ring system. Mono- or bicyclic ring systems are preferred.

Unless otherwise defined, cycloalkyl represents saturated carbocyclic radicals, optionally with other carbocyclic, fused or bridged ten rings form a polycyclic ring system.

G preferably represents oxygen or a grouping of the formula

where in each case an oxygen or sulfur atom is linked to the -CH₂ group bonded to the heterocycle,
or for a grouping of the formula

where the remainder Z is connected to Q 1,
wherein
n represents the numbers 0, 1 or 2,
Q¹ represents oxygen or sulfur,
R³ for hydrogen-cyano, optionally monosubstituted to trisubstituted by halogen, cyano and / or alkoxy having 1 to 4 carbon atoms, alkyl having 1 to 6 carbon atoms, if appropriate monosubstituted to triple by halogen, cyano and / or alkoxy having 1 to 4 carbon atoms Substituted alkoxy with 1 to 6 carbon atoms, for alkylthio with 1 to 6 carbon atoms which is optionally monosubstituted to trisubstituted by halogen, cyano and / or alkoxy with 1 to 4 carbon atoms, for optionally monosubstituted to triple by halogen, cyano and / or alkoxy 1 to 4 carbon atoms substituted alkylamino with 1 to 6 carbon atoms or for optionally up to three times substituted by halogen, cyano and / or alkoxy with 1 to 4 carbon atoms dialkylamino with 1 to 6 carbon atoms in each alkyl group or for optionally up to three times by halogen, cyano, carboxy, alkyl with 1 to 4 carbon atoms and / or alkox ycarbonyl with 1 to 4 carbon atoms in the alkoxy group substituted cycloalkyl having 3 to 6 carbon atoms, and
R⁴ for hydrogen, hydroxyl, cyano, for optionally mono- to trisubstituted by halogen, cyano and / or alkoxy with 1 to 4 carbon atoms substituted alkyl having 1 to 6 carbon atoms, for optionally mono- to triple by halogen, cyano and / or alkoxy with 1 up to 4 carbon atoms substituted alk oxy with 1 to 6 carbon atoms or cycloalkyl with 3 to 6 substituted in the alkoxy group for optionally monosubstituted to triple by halogen, cyano, carboxy, alkyl with 1 to 4 carbon atoms and / or alkoxycarbonyl with 1 to 4 carbon atoms Carbon atoms.
Q is also preferably oxygen or sulfur.
R¹ preferably represents hydrogen, straight-chain or branched alkyl having 1 to 4 carbon atoms or cycloalkyl having 3 to 8 carbon atoms.
R² preferably represents alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms or cycloalkyl having 3 to 8 carbon atoms, or
R² is preferably phenyl, naphthyl or heterocyclyl having 3 to 7 ring members, at least one of which is oxygen, sulfur or nitrogen and optionally one or two more are nitrogen, both the aromatic and the heterocyclic radicals optionally being up to four times , are identical or differently substituted by
Halogen, cyano, nitro, amino, hydroxy, formyl, carboxy, carbamoyl, thiocarbamoyl, phenyl, phenoxy;
in each case straight-chain or branched alkyl, alkoxy, alkylthio, alkylsul finyl or alkylsulfonyl each having 1 to 6 carbon atoms;
each straight-chain or branched alkenyl or alkenyloxy, each with 2 to 6 carbon atoms;
each straight-chain or branched haloalkyl, haloalkoxy, halo genalkylthio, haloalkylsulfinyl or haloalkylsulfonyl each having 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms;
each straight-chain or branched haloalkenyl or haloalkenyl oxy each having 2 to 6 carbon atoms and 1 to 11 identical or different halogen atoms;
each share straight-chain or branched alkylamino, dialkylamino, alkyl carbonyl, alkylcarbonyloxy, alkoxycarbonyl, alkoximinoalkyl or alkyl sulfonyloxy each having 1 to 6 carbon atoms in the individual alkyl;
each optionally monosubstituted to tetrasubstituted, identically or differently, by halogen, straight-chain or branched alkyl having 1 to 4 carbon atoms and / or straight-chain or branched haloalkyl having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms 3 to 6 carbon atoms or dioxyalkylene with 1 to 4 carbon atoms;
Cycloalkyl with 3 to 6 carbon atoms and / or
Heterocyclyl or heterocyclyl-methyl, each with 3 to 7 ring members, of which 1 to 3 are identical or different heteroatoms such as nitrogen, oxygen and / or sulfur.
R.sup.1 and R.sup.2 also together with the nitrogen atom to which they are bonded preferably represent a three- to seven-membered ring, which may optionally be substituted once or twice, in the same way or differently, by alkyl having 1 to 4 carbon atoms, and which also contains another oxygen , Nitrogen or sulfur atom can contain.
Y also preferably represents oxygen or sulfur.
Z preferably represents phenyl, naphthyl or heterocyclyl with 3 to 7 ring members, at least one of which is oxygen, sulfur or nitrogen and optionally one or two more are nitrogen, both the aromatic and the heterocyclic radicals optionally being up to four times, are identical or differently substituted by
Halogen, cyano, nitro, amino, hydroxy, formyl, carboxy, carbamoyl, thiocarbamoyl, phenyl, phenoxy;
each straight-chain or branched alkyl, alkoxy, alkylthio, alkyl sulfinyl or alkylsulfonyl each having 1 to 6 carbon atoms;
each straight-chain or branched alkenyl or alkenyloxy, each with 2 to 6 carbon atoms;
each straight-chain or branched haloalkyl, haloalkoxy, halo genalkylthio, haloalkylsulfinyl or haloalkylsulfonyl each having 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms;
each straight-chain or branched haloalkenyl or haloalkenyl oxy each having 2 to 6 carbon atoms and 1 to 11 identical or different halogen atoms;
each share straight-chain or branched alkylamino, dialkylamino, alkyl carbonyl, alkylcarbonyloxy, alkoxycarbonyl, alkoximinoalkyl or alkyl sulfonyloxy each having 1 to 6 carbon atoms in the individual alkyl;
each optionally monosubstituted to tetrasubstituted, identically or differently, by halogen, straight-chain or branched alkyl having 1 to 4 carbon atoms and / or straight-chain or branched haloalkyl having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms 3 to 6 carbon atoms or dioxyalkylene with 1 to 4 carbon atoms;
Cycloalkyl of 3 to 6 carbon atoms;
Heterocyclyl or heterocyclyl-methyl each having 3 to 7 ring members, of which 1 to 3 are identical or different heteroatoms such as nitrogen, oxygen and / or sulfur, and / or
by grouping the formula

wherein
A¹ represents alkyl having 1 to 4 carbon atoms or cycloalkyl having 1 to 6 carbon atoms and
A² represents alkyl having 1 to 4 carbon atoms, alkenyl having 2 to 4 carbon atoms or alkynyl having 2 to 4 carbon atoms, these radicals being mono to triple by cyano, alkoxy having 1 to 4 carbon atoms, alkylthio having 1 to 4 carbon atoms, alkylamino 1 to 4 carbon atoms, dialkylamino with 1 to 4 carbon atoms in each alkyl part and / or phenyl can be substituted.
G particularly preferably represents oxygen or a grouping of the formula

where in each case an oxygen or sulfur atom is linked to the -CH₂ group bonded to the heterocycle,
or for a grouping of the formula

where the remainder Z is connected to Q 1,
wherein
n represents the numbers 0, 1 or 2,
Q¹ represents oxygen or sulfur,
R³ represents hydrogen, cyano, methyl, ethyl, methoxy, ethoxy or cyclopropyl and
R⁴ represents hydrogen, methyl, ethyl or cyclopropyl.
Q also particularly preferably represents oxygen or sulfur.
R¹ particularly preferably represents hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, cyclopropyl, cyclopentyl or cyclohexyl.
R² particularly preferably represents methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methoxy or ethoxy or
R² particularly preferably represents phenyl, pyridinyl, pyrimidinyl or thienyl, these radicals optionally being monosubstituted to triple, identical or differently substituted by fluorine, chlorine, bromine, cyano, methyl, ethyl, n- or i-propyl, n-, i -, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- or i-propylthio, methylsulfinyl, ethyl sulfinyl, methylsulfonyl or ethylsulfonyl, trifluoromethyl, trifluorethyl, difluoromethoxy, trifluoromethoxy, difluorochloro Trifluoroethoxy, difluoromethylthio, trifluoromethylthio, difluorochloromethylthio, trifluoromethylsulfinyl or trifluoromethylsulfonyl, methoxycarbonyl, ethoxycarbonyl, methoximinomethyl, ethoximinomethyl, methoximinomethyl, ethoximinoethyl, phenyl, phenoxy,
or in each case optionally up to four times, in each case identical or different, substituted by fluorine, chlorine, methyl, trifluoromethyl or ethyl and in each case double-linked methylenedioxy, ethylenedioxy, propanediyl or butanediyl.
R¹ and R² together with the nitrogen atom to which they are attached are particularly preferably each optionally substituted once or twice by methyl or ethyl, pyrrolidinyl, piperidinyl, hexa hydroazepinyl, piperazinyl, morpholinyl or thiomorpholinyl.
Y also particularly preferably represents oxygen or sulfur.
Z particularly preferably represents phenyl, thienyl, 1,2,4-thiadiazolyl, 1,3,4-thiadiazolyl, 1,2,4-oxadiazolyl, 1,3,4-oxadiazolyl, pyridinyl, pyrimidyl, pyridazinyl, pyrazinyl, 1 , 2,3-triazinyl, 1,2,4-triazinyl or 1,3,5-triazinyl, these radicals optionally being monosubstituted to trisubstituted, identical or different, by fluorine, chlorine, bromine, cyano, methyl, ethyl, n - or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- or i-propylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl or ethylsulfonyl, Trifluoromethyl, trifluoroethyl, difluoromethoxy, trifluoromethoxy, difluorochloromethoxy, trifluorethoxy, di fluoromethylthio, trifluoromethylthio, difluorochloromethylthio, trifluoromethyl sulfinyl or trifluoromethyloxy, methoxy, methoxomethyl, methoxomethyl, methoxymethyloxy, methoxymethyl, methoxymethyl, methoxymethyl, methoxymethyl, methoxymethyl, methoxymethyl, methoxymethyl
each optionally monosubstituted to tetrasubstituted, identically or differently, by fluorine, chlorine, methyl, trifluoromethyl or ethyl and in each case doubly linked methylenedioxy, ethylenedioxy, propanediyl or butane diyl
and / or by grouping the formula

wherein
A¹ represents methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, cyclopropyl or cyclobutyl,
A² for methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, allyl, propargyl, but-2-en-1-yl, 2-methyl-prop-1-en- 3-yl, cyanomethyl, methoxymethyl, ethoxymethyl, methoxyethyl, ethoxyethyl, methylthiomethyl, ethylthiomethyl, methylthioethyl, ethylthioethyl, dimethylaminomethyl, dimethylaminoethyl, methylaminomethyl, methylaminoethyl or benzyl.

A preferred group of compounds according to the invention are heteroaryl carbonates acid amides of the formula

in which
Z, G, Q, R¹, R² and Y have the preferred or particularly preferred meanings given above.

The preferred or particularly preferred definitions given above also apply to the corresponding residues in the preliminary products or in the Intermediates are present.

The radical definitions can be among themselves, that is, between the preferred ones or particularly preferred meanings can be combined.

If 2- [1- (3 trifluoromethylphenyl) ethylidene amino oxymethyl] furan is used 3-carboxylic acid chloride and methylamine as starting materials, so the course of the method according to the invention illustrated by the following formula become light.

If one uses N-methyl-2- [1- (3-trifluoromethyl-phenyl) -ethylidene-amino-oxy methyl] -furan-3-carboxamide as the starting material and phosphorus pentasulfide as Schwe felungsreagenz, the course of the second stage of the Ver driving are illustrated by the following formula scheme.

The starting materials for carrying out the process according to the invention Required carboxylic acid halides are generally defined by the formula (II). In of this formula, G, Q and Z preferably or particularly preferably have those gen meanings already in connection with the description of the inventions compounds of the formula (I) according to the invention are preferred or are particularly preferred were preferably given for G, Q and Z. X preferably represents chlorine.

The carboxylic acid halides of the formula (II) are known in some cases (cf. Chem. Scr. (1987), 27 (3), 417-422 and Chem. Abstr. 109, 92 965).

The carboxylic acid halides of the formula

in which
R³, Q, X and Z have the meanings given above are new.

The carboxylic acid halides of the formula (IIa) can be prepared by

• a) Carboxylic acid derivatives of the formula in which
  R³, Q and Z have the meanings given above,
  with halogenating reagents, optionally in the presence of a catalyst and optionally in the presence of a diluent.
• When performing method (a) according to the invention as off Carbonic acid derivatives required for starting materials are represented by the formula (IV) generally defined. In this formula, R³, Q and Z preferably or particularly preferred those meanings that are already together hang with the description of the compounds of For mel (I) as preferred or as particularly preferred for R³, Q and Z were given.  
• The carboxylic acid derivatives of the formula (IV) are not yet known. she can be made by
• b) carboxylic acid esters of the formula in which
  R³, Q and Z have the meanings given above and
  R⁵ represents alkyl,
  with alkali metal hydroxides, optionally in the presence of a diluent, and then acidified.

Those used to carry out process (b) according to the invention as starting materials required carboxylic acid esters are generally defined by the formula (V). In of this formula, R³, Q and Z have preferred or particularly preferred those meanings that are already related to the description of the Compounds of formula (I) according to the invention as preferred or as special were preferably given for R³, Q and Z. R⁵ is preferably methyl or ethyl.

The carboxylic acid esters of the formula (V) are also not yet known. she can be made by

• c) halogen compounds of the formula in which
  Q and R⁵ have the meanings given above and
  X¹ represents halogen,
  with oximes of the formula in which
  R³ and Z have the meanings given above,
  optionally in the presence of a base and optionally in the presence of a diluent.

Those used to carry out process (c) according to the invention as starting materials Halogen compounds required are generally defined by the formula (VI). In this formula, Q and R⁵ preferably or particularly preferably have those gen meanings already in connection with the description of the inventions compounds of the formula (I) according to the invention are preferred or are particularly preferred were preferably given for Q and R⁵. X preferably represents chlorine, bromine or iodine.

The halogen compounds of formula (VI) are known and can be according to known methods are prepared (see J. Heterocycl. Chem., 1983, 1085-1088; Bull. Soc. Chim. Fr., 1974, 519 and CA: 81; 63412).

The to carry out the method (c) according to the invention as out Oximes required are generally defined by the formula (VII). In of this formula, R³ and Z preferably or particularly preferably have those Meanings already in connection with the description of the Invention  compounds of the formula (I) as preferred or as particularly preferred were given for R³ and Z.

The oximes of formula (VII) are generally known synthetic chemicals, they can follow from the corresponding ketones or aldehydes and hydroxylamine generally known methods can be produced (compare e.g. Ferry, C., Reactions of organic synthesis, Thieme Verlag, Stuttgart 1978, page 224).

All the usual anorga come as bases when carrying out process (c) niche and organic acid binders. Preferably usable are alkali metal hydrides such as sodium hydride.

All of the following are suitable as diluents when carrying out process (c) such reactions usual inert organic solvents in question. Preferential wise usable are ethers such as tetrahydrofuran and amides such as N, N-Di methylformamide, N, N-dimethylacetamide or N-methylpyrrolidone; also sulf oxides, such as dimethyl sulfoxide or sulfones, such as sulfolane.

The reaction temperatures can be carried out when carrying out process (c) can be varied within a wide range. Generally you work at temperatures between 0 ° C and 150 ° C, preferably between 20 ° C and 120 ° C.

Both when carrying out process (c) and process (a) and (b) and also in the process according to the invention for the production of hetero arylcarboxamides of the formula (I) are generally worked under Atmospheric pressure. But it is also possible in each case under increased or to work under reduced pressure.

When carrying out process (c), 1 mol of halogen is used Compound of formula (VI) in general 1 to 3 moles, preferably 1 to 2 moles of oxime of the formula (VII). The processing takes place according to usual Methods.

Alkali metal hydroxides occur when carrying out process (b) preferably sodium hydroxide or potassium hydroxide.  

All of the following are suitable as diluents when carrying out process (b) such reactions conventional organic solvents and water in question. Mixtures of water and alcohols, such as Methanol, ethanol or ethanediol.

The acids used in carrying out process (b) are all for such Implementations of conventional inorganic and organic acids. Before hydrochloric acid can also be used.

The reaction temperatures can also be carried out when carrying out process (b) can be varied within a wide range. Generally you work at temperatures between 0 ° C and 200 ° C, preferably between 20 ° C and 150 ° C.

When carrying out process (b), 1 mol of carboxylic acid ester is used of formula (V) generally an excess of alkali metal hydroxide in the form an aqueous alcoholic solution. After the implementation is acidified to Release of the carboxylic acid derivatives of the formula (IV). The workup takes place according to usual methods.

Halogenating reagents used in carrying out process (a) all components customary for the halogenation of carboxylic acids. Before Thionyl chloride, phosphorus oxychloride and phosphorus penta can also be used chloride and thionyl bromide. The corresponding iodides and fluorides can be from the chlorides or bromides by reaction with alkali metal iodides or - produce fluorides.

All of the above are used as diluents when carrying out process (a) inert organic solvents. Are preferably usable aliphatic, alicyclic or aromatic hydrocarbons, such as petroleum ether, Hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or De caline, and also halogenated hydrocarbons, such as chlorobenzene, dichlorobenzene, Dichloromethane, chloroform, carbon tetrachloride, dichloroethane or trichloroethane.

The catalysts used in carrying out process (a) are all for derar implementations usual reaction accelerators in question. Preferably ver amides such as dimethylformamide can be used.  

The reaction temperatures can also be carried out when carrying out process (a) can be varied within a wide range. Generally you work at temperatures between 0 ° C and 150 ° C, preferably between 0 ° C and 100 ° C.

When carrying out process (a), 1 mol of carboxylic acid Derivative of formula (IV) generally 1 to 1000 mol, preferably 1 to 100 moles of halogenating agent. The processing takes place according to usual Methods. In general, the procedure is such that after the implementation has ended the reaction mixture is concentrated under reduced pressure and the remaining Subject residue to a fine distillation. In many cases, the residue after concentration, without additional cleaning for further Implementations are used.

Those used to carry out the method according to the invention as a starting point Substances required amines are generally defined by the formula (III). In this Formula R¹ and R² are preferably or particularly preferably those Be interpretations already in connection with the description of the fiction moderate compounds of formula (I) as preferred or as particularly preferred for R¹ and R² have been specified.

The amines of the formula (III) are known reagents in organic chemistry.

The diluent used in the implementation of the first stage of the inventions Process according to the invention all usual inert, organic solvents in Be dress. Aliphatic, alicyclic or aromatic can preferably be used Hydrocarbons such as petroleum ether, hexane, heptane, cyclohexane, methylcyclo hexane, benzene, toluene, xylene or decalin, also halogenated hydrocarbons fe, such as chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, Dichloroethane or trichloroethane, also ethers, such as diethyl ether, diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, dioxane, tetrahydrofuran, 1,2-di methoxyethane, 1,2-diethoxyethane or anisole; furthermore ketones, such as acetone, Butanone, methyl isobutyl ketone or cyclohexanone; also nitriles, such as acetonitrile, Propionitrile, n- or i-butyronitrile or benzonitrile; moreover amides, like N, N-dimethylformamide, N, N-dimethylacetamide, N-methylformanilide, N-methyl pyrrolidone or hexamethylphosphoric triamide; further esters, such as acetic acid  methyl ester or ethyl acetate; also sulfoxides, such as dimethyl sulfoxide; also sulfones, such as sulfolane; and also alcohols, such as methanol, ethanol, n- or i-propanol, n-, i-, sec- or tert-butanol, ethanediol, propane-1,2-diol, ethoxy ethanol, methoxyethanol, diethylene glycol monomethyl ether, diethylene glycol mono ethyl ether, their mixtures with water or pure water.

The acid acceptors come into play when carrying out the first stage of the invention Process according to the invention all the usual inorganic and organic bases Question. Alkaline earth metal or alkali metal hydrides are preferably usable, hydroxides, amides, alcoholates, acetates, carbonates or bicarbonates, such as Sodium hydride, sodium amide, sodium methylate, sodium ethylate, potassium tert. butoxide, sodium hydroxide, potassium hydroxide, sodium acetate, potassium acetate, calcium acetate, sodium carbonate, potassium carbonate, potassium hydrogen carbonate and sodium hydrogen carbonate, furthermore ammonium compounds, such as ammonium hydroxide, Ammonium acetate or ammonium carbonate, and also tertiary amines, such as trimethyl amine, triethylamine, tributylamine, N, N-dimethylaniline, N, N-dimethylbenzylamine, Pyridine, N-methylpiperidine, N-methylmorpholine, N, N-dimethylaminopyridine, Di azabicyclooctane (DABCO), diazabicyclonones (DBN) or diazabicycloundecene (DBU).

The reaction temperatures can also be carried out when carrying out the first stage of The inventive method can be varied within a wide range. In general, temperatures between 0 ° C and 150 ° C, preferably between 20 ° C and 120 ° C.

When carrying out the first stage of the method according to the invention generally 0.5 to 1 mole of carboxylic acid halide of the formula (II) 15 mol, preferably 0.5 to 0.8 mol of amine of the formula (III). The processing tion takes place according to usual methods. In general, you do that if necessary, the organic phase is reduced after drying pressure is reduced.

As sulfurization reagents come when performing the second stage of The method according to the invention takes into account all the usual substances which are used in the Are able to thaw the oxygen atom of a carbonyl group against sulfur . Hydrogen sulfide can preferably be used; Phosphorus pentesulfide and Lawesson's reagent.  

The diluent used in carrying out the second stage of the inventions Process according to the invention all the usual inert, organic solvents in question. Aliphatic, alicyclic or aromatic carbons are preferably usable Hydrogen, such as petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, Benzene, toluene, xylene or decalin, also halogenated hydrocarbons, such as Chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, Di chloroethane or trichloroethane and also ethers, such as diethyl ether, diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, dioxane, tetrahydrofuran, 1,2-di methoxyethane, 1,2-diethoxyethane or anisole.

The reaction temperatures can also be carried out when carrying out the second stage of the inventive method can be varied over a wide range. in the generally one works at temperatures between 10 ° C and 180 ° C, preferably between 20 ° C and 120 ° C.

When carrying out the second stage of the method according to the invention 1 mole of amide of the formula (Ia) is generally 1 to 10 equivalents, preferably 1 to 5 equivalents of sulfurization reagent. The workup takes place according to usual methods. In general, you do that Filter the reaction mixture through a filter aid, such as diatomaceous earth, the filtrate washed with water, and the organic phase after drying beforehand reduced pressure. The remaining residue can, if necessary freed of any existing contaminants by conventional methods will.

The active compounds according to the invention have a strong microbicidal action and can be used to combat unwanted microorganisms such as fungi and Bacteria can be used practically. The active ingredients are for use as Plant protection products, particularly suitable as fungicides.

Fungicides in crop protection are used to combat plas modiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Deuteromycetes.

Bactericidal agents are used in plant protection to combat Pseudomonada ceae, Rhizobiaceae, Enterobacteriaceae, Corynebacteriaceae and Streptomycetaceae used.  

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 herpotrichoi des.

The good plant tolerance of the active ingredients in the control of the plant Concentrations necessary for diseases allow treatment from above parts of plants, planting and seeds, and the soil.

The active compounds according to the invention can be used with particularly good success Combating diseases in wine, fruit and vegetable growing, such as wise Podosphaera species, or also of rice diseases, such as Pyri cularia species can be used.

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, gra nulates, aerosols, ultra-fine encapsulations in polymeric substances and in enveloping masses for seeds, as well as ULV cold and warm mist formulations.

These formulations can be prepared in a known manner, e.g. B. by Ver mix the active ingredients with extenders, i.e. liquid solvents Pressurized liquefied gases and / or solid carriers, if necessary using surface-active agents, ie emulsifiers and / or Dispersing agents and / or foaming agents. In case of use of water as an extender can e.g. B. also organic solvents as auxiliary sol be used. The liquid solvents come essentially Chen in question: aromatics such as xylene, toluene or alkylnaphthalenes, chlorinated aro mate or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chlorine ethylene or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, e.g. 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 cyclohexanone, strongly polar solvents such as dimethylformamide and Dimethyl sulfoxide, and water. With liquefied gaseous extenders or Carriers are meant liquids which are at normal temperature and are gaseous under normal pressure, e.g. B. aerosol propellants such as Halenkenkoh Hydrogen oils as well as butane, propane, nitrogen and carbon dioxide. As a firm dream Gerstoffe come into question: z. B. natural stone powder, such as kaolins, clays, Talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and syn thetic rock powder, such as highly disperse silica, aluminum oxide and silica te. Possible solid carriers for granules are: B. broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite  as well as synthetic granules from inorganic and organic flours and Granules made of organic material such as sawdust, coconut shells, corn cobs and tobacco stems. As emulsifiers and / or foaming agents come in Question: e.g. B. non-ionic and anionic emulsifiers, such as polyoxyethylene fat acid esters, polyoxyethylene fatty alcohol ethers, e.g. B. alkylaryl polyglycol ether, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates. As a disperser middle come into question: z. B. lignin sulfite and methyl cellulose.

Adhesives such as carboxymethyl cellulose, natural, can be used in the formulations Liche and synthetic powdery, granular or latex-shaped polymers used such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural Phospholipids such as cephalins and lecithins, and synthetic phospholipids. Other additives can be mineral and vegetable oils.

Dyes such as inorganic pigments, e.g. B. iron oxide, titanium oxide, Ferrocyan blue 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% by weight zent active ingredient, preferably between 0.5 and 90%.

The active compounds according to the invention can be used as such or in their formulation also in a mixture with known fungicides, bactericides, acaricides, nema ticides or insecticides are used, e.g. B. to spread the spectrum of activity t or prevent 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

2-aminobutane; 2-anilino-4-methyl-6-cyclopropyl-pyrimidine; 2 ′, 6′-dibromo-2-methyl-4′-trifluoromethoxy-4′-trifluoromethyl-1,3-thiazole-5-carboxane-ilide; 2,6-di chloro-N- (4-trifluoromethylbenzyl) benzamide; (E) -2-methoxyimino-N-methyl-2- (2-phenoxyphenyl) acetamide; 8-hydroxyquinoline sulfate; Methyl- (E) -2- {2- [6- (2-cyanophenoxy) pyrimidin-4-yloxy] phenyl} -3-methoxyacrylate; Methyl (E) methoximino [alpha- (o-tolyloxy) -o-tolyl] acetate; 2-phenylphenol (OPP), aldimorph, ampropylfos, anilazine, azaconazole,
Benalaxyl, Benodanil, Benomyl, Binapacryl, Biphenyl, Bitertanol, Blasticidin-S, Bromuconazole, Bupirimate, Buthiobate,
Calcium polysulfide, captafol, captan, carbendazim, carboxin, quinomethionate (quinomethionate), chloroneb, chloropicrin, chlorothalonil, chlozolinate, cufraneb, cymoxanil, cyproconazole, cyprofuram,
Dichlorophen, diclobutrazole, diclofluanid, diclomezin, dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomorph, diniconazole, dinocap, diphenylamine, dipyrithione, ditalimfos, dithianon, dodine, drazoxolon, epimolazone, edifenazolone, edifenazolone, edifenazolone, edifenazolone, edifenazole
Fenarimol, Fenbuconazole, Fenfuram, Fenitropan, Fenpiclonil, Fenpropidin, Fen propimorph, Fentinacetat, Fentinhydroxyd, Ferbam, Ferimzone, Fluazinam, Fludioxonil, Fluoromide, Fluquinconazole, Flusilazole, Flusulfamide, Flutolanyl, Futuberolosil, Futuberfosil , Furmecyclox,
Guazatine,
Hexachlorobenzene, hexaconazole, hymexazole,
Imazalil, Imibenconazol, Iminoctadin, Iprobefos (IBP), Iprodion, Isoprothiolan, Kasugamycin, copper preparations like. Copper hydroxide, copper naphthenate, copper oxychloride, copper sulfate, copper oxide, oxine copper and Bordeaux mixture,
Mancopper, Mancozeb, Maneb, Mepampynm, Mepronil, Metalaxyl, Metconazol, Methasulfocarb, Methfuroxam, Metiram, Metsulfovax, Myclobutanil, Nickel-dimethyldithiocarbamat, Nitrothal-isopropyl, Nuarimol, Ofurace, Oxadoxinoxoxoxoxoxoxamoxamoxam
Pefurazoate, penconazole, pencycuron, phosdiphen, pimaricin, piperalin, polyoxin, probenazole, prochloraz, procymidon, propamocarb, propiconazole, propineb, pyr azophos, pyrifenox, pyrimethanil, pyroquilon,
Quintozen (PCNB),
Sulfur and sulfur preparations,
Tebuconazole, Tecloftalam, Tecnazen, Tetraconazole, Thiabendazole, Thicyofen, Thio phanat-methyl, Thiram, Tolclophos-methyl, Tolylfluanid, Triadimefon, Tria dimenol, Triazoxid, Trichlamid, Tricyclazol, Tridemorph, Triflorolizol, Triflorolizol, Triflorolizol
Validamycin A, vinclozolin,
Zineb, ziram

Bactericides

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

Insecticides / acaricides / nematicides

Abamectin, Acephat, Acrinathrin, Alanycarb, Aldicarb, Alphamethrin, Amitraz, Avermectin, AZ 60541, Azadirachtin, Azinphos A, Azinphos M, Azocyclotin, Bacillus thuringiensis, 4-Bromo-2- (4-chlorophenyl) -1- (ethoxymethyl 5- (trifluoro methyl) - 1H-pyrrole-3-carbonitrile, Bendiocarb, Benfuracarb, Bensultap, Betacyflu thrin, Bifenthrin, BPMC, Brofenprox, Bromophos A, Bufencarb, Buprofezin, Buto carboxin, Butylpyridaben,
Cadusafos, Carbaryl, Carbofuran, Carbophenothion, Carbosulfan, Cartap, Chloetho carb, Chlorethoxyfos, Chloretoxyfos, Chlorfenvinphos, Chlorfluazuron, Chlorme phos, N - [(6-Chloro-3-pyridinyl) -methyl] -N'-cyano-N-methyl -ethanimidamide, chloropyrifos, chlorpyrifos M, cis-resmethrin, clocythrin, clofentezin, cyanophos, cycloprothrin, cyfluthrin, cyhalothrin, cyhexatin, cypermethrin, cyromazine, deltamethrin, demeton M, demeton S, diafonethonon , Dichlorvos, dicliphos, dicrotophos, diethion, diflubenzuron, dimethoate,
Dimethylvinphos, dioxathione, disulfoton,
Edifenphos, Emamectin, Esfenvalerat, Ethiofencarb, Ethion, Ethofenprox, Ethopro phos, Etrimphos,
Fenamiphos, Fenazaquin, Fenbutatinoxid, Fenitrothion, Fenobucarb, Fenothiocarb, Fenoxycarb, Fenpropathrin, Fenpyrad, Fenpyroximat, Fenthion, Fenvalerate, Fipronil, Fluazinam, Fluazuron, Flucycloxuron, Flucythrinat, Flufenoxurosinofionfonfonofionfonofinfonofin, fufenionophonate, fufonoxuroninfonofionfonofionfonofionfonofionfonofionfonofinofinofinfonofinofionofinfonofinofinofinfonofinofinofinfonofinofionofinfonofinofinofionofinfonofinofionofinfonofinofinofinofinofoxinoxinox , HCH, Heptenophos, Hexaflumuron, Hexythiazox,
Imidacloprid, Iprobefos, Isazophos, Isofenphos, Isoprocarb, Isoxathion, Ivermectin,
Lambda cyhalothrin, lufenuron,
Malathion, Mecarbam, Mervinphos, Mesulfenphos, Metaldehyde, Methacrifos, Metamidophos, Methidathion, Methiocarb, Methomyl, Metolcarb, Milbemectin, Monocrotophos, Moxidectin,
Naled, NC 184, Nitenpyram
Omethoate, Oxamyl, Oxydemethon M, Oxydeprofos,
Parathion A, Parathion M, Permethrin, Phenthoat, Phorat, Phosalon, Phosmet, Phosphamidon, Phoxim, Pirimicarb, Pirimiphos M, Pirimiphos A, Profenofos, Promecarb, Propaphos, Propoxur, Prothiofos, Prothiophos, Prothoat, Pymetrohine, Pyrymophone, Pyromicro Pyrethrum, Pyridaben, Pyrimidifen, Pyriproxifen,
Quinalphos,
Salithion, Sebufos, Silafluofen, Sulfotep, Sulprofos,
Tebufenozide, Tebufenpyrad, Tebupirimiphos, Teflubenzuron, Tefluthrin, Teme phos, Terbam, Terbufos, Tetrachlorvinphos, Thiafenox, Thiodicarb, Thiofanox, Thiomethon, Thionazin, Thuringiensin, Tralomenhriazon, Tralomenhronon, Tronomenhrononium , Zetamethrin.

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

The active compounds according to the invention can, as such, in the form of their commercially available Chen formulations or the application forms prepared from them, such as ready-to-use solutions, suspensions, wettable powders, pastes, soluble powders, Dusts and granules can be used. The application happens in usual way, e.g. B. by pouring, spraying, spraying, scattering, Ver foaming, brushing etc. . If necessary, the active ingredients after Ultra-low-volume process applied or the drug preparation or the Active ingredient itself is injected into the soil. If necessary, also the seeds of the plants treated.

When treating parts of plants, the active substance concentrations can be in the application forms can be varied in a larger area: generally between 1 and 0.0001% by weight, preferably between 0.5 and 0.001% by weight.  

In the seed treatment, amounts of active ingredient are generally from 0.001 to 50 g per kilogram of seed, preferably 0.01 to 10 g.

When treating the soil, active ingredient concentrations are from 0.00001 to 0.1 wt .-%, preferably from 0.0001 to 0.02 wt .-% at the place of action such.

The preparation and use of active compounds according to the invention are illustrated by the following examples.

Manufacturing examples example 1

2.1 g of 2- [1- (3-trifluoromethylphenyl) ethylidene aminooxymethyl] furan-3-carboxylic acid re (6 mmol) are dissolved in 50 ml dichloroethane and at room temperature with 1.53 g (20 mmol) of thionyl chloride (20 mmol) were added. You heat for an hour under reflux and then the solution is concentrated under reduced pressure. The ver permanent residue of 2- [1- (3-trifluoromethylphenyl) ethylidene aminooxy methyl] -furan-3-carboxylic acid chloride is taken up in 50 ml of dichloromethane. The resulting solution becomes 50 ml at room temperature with stirring 20% aqueous methylamine solution added dropwise. After an hour the separated organic phase, dried over sodium sulfate and with reducing reduced pressure.

1.7 g (83% of theory) of N-methyl-2- [1- (3-trifluoromethylphenyl) ethylidene-aminooxymethyl] furan-3-carboxamide are obtained.
1 H-NMR (CDCl₃ / TMS): δ = 2.25 (s, 3H), 2.92 (d, 3H) ppm

Production of the starting material

A solution of 5 g of 2- [1- (3-trifluoromethylphenyl) ethylidene aminooxymethyl] furan-3-carboxylic acid methyl ester (14.5 mmol) in 50 ml of methanol is at room 1.15 g (29 mmol) of sodium hydroxide were added with stirring. Man the solution is heated under reflux for 2 hours, then the methanol is distilled in reduced pressure, dissolves the solid obtained in 60 ml of water and drips 3 g concentrated hydrochloric acid. After 10 minutes, the resulting solid vacuumed and dried.

8.4 g (98% of theory) of 2- [1- (3-trifluoromethylphenyl) ethylidene aminooxymethyl] furan-3-carboxylic acid are obtained.
GC / MS (silylated): M⁺ (sil) = 399

Production of the preliminary product

A solution of 8.1 g (40 mmol) of 3-trifluoromethylacetophenone oxime in 50 ml of Di methylformamide becomes a suspension of at room temperature with stirring 1.4 g (40 mmol) of 80% sodium hydride in 30 ml of dimethylformamide. After 30 minutes, a solution of 8.8 g is added dropwise to this mixture (40 mmol) methyl 2-bromomethyl-3-furanecarboxylate in 20 ml dimethyl form amid. After a reaction time of 14 hours, the reaction mixture is poured into 150 ml 10% hydrochloric acid and 200 ml methyl t-butyl ether, separates the organic phase, dries over magnesium sulfate and concentrates under reduced pressure.

11.4 g (83% of theory) of 2- [1- (3-trifluoromethylphenyl) ethylidene aminooxymethyl] furan-3-carboxylic acid methyl ester are obtained.
1 H-NMR: 2.25 (s, 3H), 3.87 (s, 3H), 5.51 (s, 2H)

Example 2

A solution of 1 g (2.94 mmol) of N-methyl-2- [1- (3-trifluoromethylphenyl) ethylidene-aminooxymethyl] furan-3-carboxamide in 50 ml of toluene is stirred at room temperature with 0. 16 g (0.36 mmol) of phosphorus pentasulfide were added. The mixture is heated under reflux for one hour and the mixture is filtered through diatomaceous earth. The filtrate is washed with water. The organic phase is dried over magnesium sulfate and concentrated under reduced pressure. 0.8 g (76% of theory) of N-methyl-2- [1- (3-trifluoromethylphenyl) ethylidene-aminooxymethyl] furan-3-thiocarboxamide is obtained as the residue.
1 H-NMR (CDCl₃ / TMS): = 2.33 (s, 3H), 3.17 (d, 3H), 5.19 (s, 2H) ppm

According to the methods given above, those in the following are also obtained Compounds of the formula according to the invention listed in Table 1:

Table 1

According to the methods given above, those in the following are also obtained Compounds of formula (IV) according to the invention listed in Table 2.  

Table 2

According to the methods given above, those in the following are also obtained Compounds of formula (V) according to the invention listed in Table 3.  

Table 3

Examples of use Example A

Pyricularia test (rice) / protective
Solvent: 12.5 parts by weight of acetone
Emulsifier: 0.3 part by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, 1 Ge is mixed most of the active ingredient with the specified amounts of solvent and dilutes the Concentrate with water and the specified amount of emulsifier to the desired concentration.

To test for protective effectiveness, young rice plants are sprayed with the Active ingredient preparation to dripping wet. 5 days after the treatment Plants inoculated with an aqueous spore suspension of Pyricularia oryzae. The plants are then in a greenhouse at 100% rel. Air humidity and 25 ° C.

The disease infestation is evaluated 4 days after the inoculation. Here 0% means an efficiency which corresponds to that of the control, while an efficiency of 100% means that no infection is observed.

In this test, the inventions disclosed in Examples 5, 9, 10 and 23 show substances according to the invention with an active ingredient concentration in the spray mixture of 0.025% an efficiency of at least 70%.  

Example B

Podosphaera test (apple) / protective
Solvent: 4.7 parts by weight of acetone
Emulsifier: 0.3 part by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, 1 Ge is mixed most of the 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 to dripping wet. After the spray coating has dried on the plants are pollinated with conidia of the powdery mildew pathogen Podosphaera leucotricha inoculated.

The plants are then grown in a greenhouse at 23 ° C and relative air humidity of approx. 70%.

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

In this test, those disclosed in Examples 2 and 35 show substances according to the invention at an active substance concentration in the spray liquid of 100 ppm an efficiency of over 80%.

Claims (12)

1. Heteroaylcarboxamides of the formula in which
G for oxygen or a grouping of the formula stands, with the oxygen or
Sulfur atom is linked to the -CH₂- group attached to the heterocycle,
or for a grouping of the formula stands,
where the remainder Z is connected to Q 1,
in which
n represents the numbers 0, 1 or 2,
Q¹ represents oxygen or sulfur,
R³ represents hydrogen, cyano or in each case optionally substituted alkyl, alkoxy, alkylthio, alkylamino, dialkylamino or cycloalkyl, and
R⁴ represents hydrogen, hydroxy, cyano or in each case optionally substituted alkyl, alkoxy or cycloalkyl,
Q represents oxygen or sulfur,
R¹ represents hydrogen, alkyl or cycloalkyl,
R² represents alkyl, alkoxy, cycloalkyl, optionally substituted aryl or optionally substituted heterocyclyl,
or R¹ and R² together with the nitrogen atom to which they are attached form an optionally substituted heterocyclic ring,
Y stands for oxygen or sulfur and
Z stands for optionally substituted aryl or heterocyclyl. 2. A process for the preparation of heteroarylcarboxamides of the formula (I) according to Claim 1, characterized in that carboxylic acid halides of the formula in which
G, Q and Z have the meanings given above and
X represents halogen,
with amines of the formula in which
R¹ and R² have the meanings given above,
if appropriate in the presence of an acid acceptor and if appropriate in the presence of a diluent and if appropriate the resulting amides of the formula in which
G, Q, R¹, R² and Z have the meanings given above,
with a sulfurization reagent, optionally in the presence of a diluent. 3. Means to combat unwanted microorganisms, labeled by the content of at least one heteroarylcarboxamide Formula (I) according to claim 1. 4. Use of heteroarylcarboxamides of the formula (I) according to Claim 1 to combat unwanted microorganisms. 5. Process for combating undesirable microorganisms, thereby characterized in that heteroarylcarboxamides of the formula (I) according to claim 1 on the microorganisms and / or their habitat deploys. 6. Process for the preparation of agents for combating undesirable Microorganisms, characterized in that heteroaryl carbon  Acid amides of the formula (I) according to Claim 1 with extenders and / or surface-active substances mixed. 7. Carboxylic acid halides of the formula in which
R³ represents hydrogen, cyano or in each case optionally substituted alkyl, alkoxy, alkylthio, alkylamino, dialkylamino or cycloalkyl,
Q represents oxygen or sulfur,
X represents halogen and
Z stands for optionally substituted aryl or heterocyclyl. 8. A process for the preparation of carboxylic acid halides of the formula (IIa) according to claim 7, characterized in that

• a) Carboxylic acid derivatives of the formula in which
  R³, Q and Z have the meanings given above,
  with halogenating reagents, if appropriate in the presence of a catalyst and if appropriate in the presence of a diluent.

9. Carboxylic acid derivatives of the formula in which
R³ represents hydrogen, cyano or in each case optionally substituted alkyl, alkoxy, alkylthio, alkylamino, dialkylamino or cycloalkyl,
Q stands for oxygen or sulfur and
Z stands for optionally substituted aryl or heterocyclyl. 10. A process for the preparation of carboxylic acid derivatives of the formula (IV) according to claim 9, characterized in that

• b) carboxylic acid esters of the formula in which
  R³, Q and Z have the meanings given above and
  R⁵ represents alkyl,
  with alkali metal hydroxides, optionally in the presence of a diluent, and then acidified.

11. Carboxylic acid esters of the formula in which
R³ represents hydrogen-cyano or optionally substituted alkyl, alkoxy, alkylthio, alkylamino, dialkylamino or cycloalkyl,
R⁵ represents alkyl,
Q stands for oxygen or sulfur and
Z stands for optionally substituted aryl or heterocyclyl. 12. A process for the preparation of carboxylic acid esters of the formula (V) according to claim 11, characterized in that

• c) halogen compounds of the formula in which
  Q and R⁵ have the meanings given above and
  X¹ represents halogen,
  with oximes of the formula in which
  R³ and Z have the meanings given above,
  optionally in the presence of a base and optionally in the presence of a diluent.