EP1697329A1

EP1697329A1 - Optically active carboxamides and use thereof to combat undesirable microorganisms

Info

Publication number: EP1697329A1
Application number: EP04803543A
Authority: EP
Inventors: Ralf Dunkel; Hans-Ludwig Elbe; Heiko Rieck; Benoit Hartmann; Jörg Nico GREUL; Ulrike Wachendorff-Neumann; Peter Dahmen; Karl-Heinz Kuck; Anne Suty-Heinze
Original assignee: Bayer CropScience AG
Current assignee: Bayer CropScience AG
Priority date: 2003-12-18
Filing date: 2004-12-06
Publication date: 2006-09-06
Also published as: AR047148A1; US20070276022A1; MXPA06006744A; AU2004299217A1; JP2007516261A; KR20060126713A; CA2549821A1; BRPI0417616A; WO2005058839A1

Abstract

Novel optically active carboxamides of formula (1) wherein R, M and A have the meanings cited in the description, several methods for the production of said substances and the use thereof to combat undesirable microorganisms, in addition to novel intermediate products and the production thereof.

Description

OPTICALLY ACTIVE CARBOXAMIDES AND THEIR USE FOR COMBATING UNWANTED MICROORGANISMS

The present invention relates to new optically active carboxamides, several processes for their preparation and their use for controlling unwanted microorganisms.

It is already known that numerous carboxamides have fungicidal properties (cf., for example, WO 03/010149, WO 02/059086, WO 02/38542, WO 00/09482, DE-A 10229595, EP-A 0 591 699, EP-A 0 589 301 and EP-A 0 545 099). For example, the acemates of 5-fluoro-1,3-dimethyl-N- [2- (1,3,3-trimethylbutyl) phenyl] -lH-pyrazole-4-carboxarrιid from WO 03/010149 and N- [2- (l , 3-Dimethylbutyl) - phenyl] -2-iodbenza id known from DE-A 10229 595. The effectiveness of these substances is good, but leaves something to be desired in some cases at low application rates.

Because of the diverse requirements placed on modern pesticides, for example in terms of potency, duration, potency, application spectrum, toxicity, combination with other active compounds, combination with formulation auxiliaries or synthesis, and because of the possible occurrence of resistance, the development of such compounds can never be considered be considered complete, and there is a constant high demand for new connections, which bring advantages at least in part over the known connections.

New optically active carboxamides of the formula (I)

found in which

R represents hydrogen, fluorine, chlorine, methyl, ethyl or trifluoromethyl,

wherein the bond marked with * is linked to the amide, while the bond marked with # is linked to the alkyl side chain, R ^{1 represents} hydrogen, fluorine, chlorine, methyl or trifluoromethyl,

A for the rest of the formula (AI) (AI) is in which R ^{2 represents} methyl, trifluoromethyl or difluoromethyl, R ^{3 represents} hydrogen, fluorine or chlorine, or A represents the rest of the formula (A2)

(A2) stands in which R ^{4 represents} trifluoromethyl, chlorine, bromine or iodine, or

A for the rest of formula (A3)

(A3) stands in which R ^{5 represents} methyl, trifluoromethyl or difluoromethyl.

The compounds of formula (I) have the S configuration [S atom labeled C in formula (I)].

Furthermore, it was found that optically active carboxamides of the formula (I) are obtained by a) carboxylic acid derivatives of the formula (H) O Λ .Λ- -x, 'W in which A has the meanings given above and X ¹ for Halogen or hydroxy, with an amine of the formula (Hl)

in which R and M have the meanings given above, if appropriate in the presence of a catalyst, if appropriate in the presence of a condensing agent, if appropriate in the presence of an acid binder and if appropriate in In the presence of a diluent, or b) racemic compounds of the formula (I-rac)

in which R, M and A have the meanings given above, chromatographed on a chiral stationary silica gel phase in the presence of an eluent or an eluent mixture as the liquid phase, or fractionally crystallized with optically active acids with salt formation and then the enantiomerically pure or enriched compounds of the formula (I) releases, or c) compounds of the formula (IV)

in which R, M and A have the meanings given above, or compounds of the formula (V)

in which R, M and A have the meanings given above, or mixtures of both compounds in the presence of an optically active catalyst or a catalyst with optically active ligand.

Finally, it was found that the new optically active carboxamides of the formula (I) have very good microbicidal properties and can be used to combat unwanted microorganisms both in crop protection and in material protection.

Compared to known carboxamides, the new optically active carboxamides of the formula (I) are notable in particular for their improved action or lower application rate and thus lower environmental impact and reduced toxicity.

The optically active carboxamides according to the invention are generally defined by the formula (I). Preferred radical definitions of the formulas above and below are given in Given below. These definitions apply equally to the end products of the formula (I) and to all intermediates.

R preferably represents hydrogen, methyl or ethyl. R particularly preferably represents hydrogen or methyl.

M preferably stands for M-1.

M also preferably represents M-2.

M also preferably stands for M-3. M also preferably represents M-4.

M particularly preferably represents Ml, where R ^{1 represents} hydrogen.

M is also particularly preferably M-2, where R ^{1 is} hydrogen.

R ¹ preferably represents hydrogen. R ¹ also preferably represents fluorine, fluorine being particularly preferably in the 4-, 5- or 6-position, very particularly preferably in the 4- or 6-position, in particular in the 4-position of the anilide residue [cf. formula (I) above].

A preferably represents the radical A 1. A particularly preferably represents Al with the meaning 5-fluoro-1,3-dimethyl-1H-pyrazol-4-yl, 3-trifluoromethyl-1-methyl-1 H-pyrazole-4 -yl or 3-difluoromethyl-1-methyl-1 H-pyrazol-4-yl. A very particularly preferably represents Al with the meaning 5-fluoro-1,3-dimethyl-1H-pyrazol-4-yl.

A also preferably represents the radical A2.

A particularly preferably represents A2 with the meaning 2-trifluoromethylphenyl or 2-iodophenyl.

A also preferably stands for the rest A3. A particularly preferably represents A3 with the meaning 1,4-dimethyl-pyrazol-3 "-yl, l-methyl-4-trifluoromethyl-pyrazol-3-yl or l-methyl-4-difluoromethyl-pyrazol-3-yl. A very particularly preferably represents A3 with the meaning l-methyl-4-trifluoromethyl-pyrazol-3-yl.

R ² preferably represents methyl or trifluoromethyl. R ³ preferably represents hydrogen or fluorine. R ⁴ preferably represents trifluoromethyl or iodine.

R ⁵ preferably represents trifluoromethyl.

However, the general definitions or explanations of residues or explanations listed above or in preferred areas can also be combined with one another as desired, that is to say between the respective areas and preferred areas. They apply accordingly to the end products as well as to the preliminary and intermediate products.

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

Preferred, particularly preferred or very particularly preferred are compounds of the formula (T) which each carry the substituents mentioned under preferred, particularly preferred or very particularly preferred.

Explanation of the processes and intermediates Process (a)

If 1-methyl-4- (trifluoromethyl) -lH-pyrrole-3-carbonyl chloride and {2 - [(IS) -l, 3,3-trimethylbutyl] phenyl} amine are used as starting materials, the invention can Process (a) can be illustrated by the following formula scheme:

Formula (H) provides a general definition of the carboxylic acid derivatives required as starting materials for carrying out process (a) according to the invention. In this formula (H), A has preferred, particularly preferred or very particularly preferred those meanings which have already been given as preferred, particularly preferred or very particularly preferred for A in connection with the description of the compounds of the formula (I) according to the invention. X ¹ preferably represents chlorine, bromine or hydroxy, particularly preferably chlorine.

The carboxylic acid derivatives of the formula (H) are known (cf. WO 93/11117, EP-A 0 545 099, EP-A 0 589 301 and EP-A 0 589 313). Formula (IH) provides a general definition of the amines which are further required as starting materials for carrying out process (a) according to the invention. In this formula (HT), R and M have preferred, particularly preferably or very particularly preferably those meanings which, in connection with the description of the compounds of the formula (I) according to the invention, are preferred, particularly preferred or very particularly preferred for these radicals were specified.

The amines of the formula (IH) are new.

Amines of the formula (Tü-a)

in which

R has the meanings given above,

M ^{1 represents} Ml can be prepared, for example, by d) in a first step an aniline derivative of the formula (VI)

in which R ^{1 has} the meanings given above, with an alkene of the formula (VH) in which R has the meanings given above, in the presence of a catalyst, if appropriate in the presence of a base and if appropriate in the presence of a diluent, and the alkenaniline of the formula (VTH) thus obtained

in which R and R ^{1 have} the meanings given above, hydrogenated in a second step, if appropriate in the presence of a diluent and if appropriate in the presence of a catalyst, and the racemic aniline derivative of the formula (HI-a-rac) thus obtained

in which R and R ^{1 have} the meanings given above, in a third step, chromatographed on a chiral stationary silica gel phase in the presence of an eluent or an eluent mixture as the liquid phase.

The hydrogenation of compounds of the formula (VIH) can, if appropriate, also take place in the presence of an optically active catalyst or in the presence of a catalyst and an optically active ligand and thus provide optically active compounds of the formula (Hl-a).

Compounds of the formula (Tü-a-rac) can also be fractionally crystallized in the presence of optically active acids with salt formation, after which enantiomerically pure or enriched compounds of the formula (HI-a) are released. All optically active acids are generally suitable as acids for the formation of diastereomeric salts. Examples include: (IS) - (+) - camphor-10-sulfonic acid, (1R) - (-) - camphor-10-sulfonic acid, S, S - (-) - tartaric acid, R, R - (+) - Tartaric acid, R-lactic acid, S-lactic acid or optically active amino acids, preferably naturally occurring optically active amino acids.

Formula (VI) provides a general definition of the aniline derivatives required as starting materials for carrying out process (d) according to the invention. In this formula (VI), R ^{1 has} preferred, particularly preferably or very particularly preferably those meanings which, in connection with the description of the compounds of the formula (I) according to the invention, are preferred, particularly preferred or very particularly for these radicals were given preferably.

Aniline derivatives of the formula (VI) are known.

Formula (VH) provides a general definition of the alkenes still required as starting materials for carrying out process (d) according to the invention. In this formula (VH), R preferably, particularly preferably or very particularly preferably those meanings which have already been given as preferred, particularly preferred or very particularly preferred for this radical in connection with the description of the compounds of the formula (I) according to the invention ,

Alkenes of the formula (VH) are known or can be obtained by known methods. The formula (VuT) generally defines the alkenanilines which have passed through as intermediates when carrying out process (d) according to the invention. In this formula (VΩΣ) R and R ^{1 have} preferred, particularly preferably or very particularly preferably those meanings which, in connection with the description of the compounds of the formula (I) according to the invention, are preferred, particularly preferred or very particularly for these radicals were given preferably.

Alkenanilines of the formula (VEIT) are known and / or can be obtained by known processes.

The amines of the formula (Hi-b)

^H CH ₃ CH ₃ in which

R has the meanings given above,

M ^{2 stands} for M-2, M-3 or M-4, can be prepared, for example, by e) racemic amines of the formula (Hl-b-rac)

in which R and M ^{2 have} the meanings given above, chromatographed on a chiral stationary silica gel phase in the presence of an eluent or of an eluent mixture as the liquid phase.

The racemic amines of the formula (Hl-b-rac) are known and / or can be obtained by known processes (cf. e.g. WO 02/38542, EP-A 1 036793 and EP-A 0 737 682).

Method (b)

The formula (I-rac) provides a general definition of the racemic compounds required as starting materials when carrying out process (b) according to the invention. In this formula, R, M and A are preferably, particularly preferably or very particularly preferably those meanings which, in connection with the description of the compounds of the formula (I) according to the invention, are preferred, particularly preferred or very particularly preferred for these radicals were called. The racemic compounds of the formula (I-rac) used in carrying out process (b) according to the invention are known and can be prepared by known processes (cf., for example, WO 03/010149, WO 02/38542 and DE-A 10229 595). Racemic compounds of the formula (I-rac) can be obtained, for example, by comparing carboxylic acid derivatives of the formula (H) with racemic compounds of the formulas (IH-a-rac) or (Hl-b-rac) in analogy to that implementing method (a) according to the invention.

The method (b) according to the invention is carried out by preparative chromatography methods, preferably by the high performance liquid chromatography (HPLC) method. A chiral stationary silica gel phase is used. Chiracel OD ^{® has} proven to be particularly suitable for the separation of the compounds of the formula (I-rac) into the two enantiomers. This separation material is commercially available. However, other stationary phases can also be used as the chromatography material.

If compounds of the formula (I-rac) are to be separated into the individual optically active compounds by means of fractional crystallization, all optically active acids are generally suitable for the formation of diastereomeric salts. Examples include: (IS) - (+) - camphor-10-sulfonic acid, (IR) - (-) - camphor-10-sulfonic acid, S, S - (-) - tartaric acid, R, R - (+) - Tartaric acid, R-lactic acid, S-lactic acid or optically active amino acids, preferably naturally occurring optically active amino acids.

Procedure (c)

If one uses N- [2- (1,3-dimethylbut-1-en-1-yl) phenyl] -5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide, hydrogen and an optically active Catalyst as starting materials, process (c) according to the invention can be illustrated by the following formula:

Formula (IV) and (V) provide a general definition of the compounds required as starting materials when carrying out process (c) according to the invention. In these formulas, R, M and A have preferably, particularly preferably or very particularly preferably those meanings which have already been mentioned as preferred, particularly preferred or very particularly preferred for these radicals in connection with the description of the compounds of the formula (I) according to the invention were. Compounds of the formula (TV) and (V) (or mixtures of these compounds) are obtained by f) carboxylic acid derivatives of the formula H) in which A has the meanings given above and X ^{1 represents} halogen or hydroxy, either with an alkenaniline of the formula (VTfl)

in which R and R ^{1 have} the meanings given above, or with an alkenaniline of the formula (TX)

in which R and R ^{1 have} the meanings given above, if appropriate in the presence of a catalyst, if appropriate in the presence of a condensing agent, if appropriate in the presence of an acid binder and if appropriate in the presence of a diluent, or g) carboxamides of the formula (X)

in which M and A have the meanings given above and Y represents bromine or iodine, with an alkene of the formula (Vπ) in which R has the meanings given above, or an alkene of the formula (XI) in which R has the meanings given above, in the presence of a catalyst, optionally in the presence of a base and, if appropriate, in the presence of a diluent.

The carboxylic acid derivatives of the formula (H) required as starting materials for carrying out process (f) according to the invention have already been described in connection with process (a).

The alkenanilines of the formula (VIII) which are further required as starting materials for carrying out process (f) according to the invention have already been described in connection with process (d).

Formula (TX) provides a general definition of the alkenanilines which are alternatively required as starting materials for carrying out process (f) according to the invention. In this formula (DC) R and R ^! preferred, particularly preferred or very particularly preferred those meanings which are already in connection with the description of the compounds of the formula according to the invention

(I) for these radicals as preferred, particularly preferred or very particularly preferred.

Alkenanilines of the formula (IX) are known and / or can be obtained by known processes.

Formula (X) provides a general definition of the carboxamides required as starting materials for carrying out process (g) according to the invention. In this formula (X), M and A have preferred, particularly preferably or very particularly preferably those meanings which, in connection with the description of the compounds of the formula (I) according to the invention, are preferred, particularly preferred or very particularly preferred for these radicals were specified.

Carboxamides of the formula (X) are known and / or can be obtained by known methods (cf. WO 03/010149).

The alkenes of the formula (VH) which are furthermore required as starting materials for carrying out process (g) according to the invention have already been described in connection with process (d). Formula (XI) provides a general definition of the alkenes alternatively required as starting materials for carrying out process (g) according to the invention. In this formula (XT), R preferably, particularly preferably or very particularly preferably those meanings which have already been given as preferred, particularly preferred or very particularly preferred for this radical in connection with the description of the compounds of the formula (I) according to the invention ,

Alkenes of the formula (XT) are known or can be obtained by known methods.

Reaction conditions Suitable diluents for carrying out processes (a) and (f) according to the invention are all inert organic solvents. These preferably include aliphatic, alicyclic or aromatic hydrocarbons, such as e.g. Petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin; halogenated hydrocarbons, e.g. Chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane or trichloroethane; Ethers, such as diethyl ether, diisopropyl ether, methyl tert-butyl ether, methyl tert-amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane or anisole or amides, such as N, N-dimethylformamide, N, N- Dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric triamide.

Processes (a) and (f) according to the invention are optionally carried out in the presence of a suitable acid acceptor. All conventional inorganic or organic bases are suitable as such. These preferably include alkaline earth metal or alkali metal hydrides, hydroxides, amides, alcoholates, acetates, carbonates or hydrogen carbonates, such as e.g. Sodium hydride, sodium amide, sodium methylate, sodium ethylate, potassium tert-butoxide, sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium acetate, potassium acetate, calcium acetate, ammonium acetate, sodium carbonate, potassium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate or ammonium carbonate, and also tertiary amines such as trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, N, N-dimethylbenzylamine, pyridine, N-methylpiperidine, N-methylmo holin, N, N-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclonones (DBN) or diazabicyclound (DBU).

Processes (a) and (f) according to the invention are optionally carried out in the presence of a suitable condensing agent. All condensation agents that can normally be used for such amidation reactions are suitable as such. Acid halide formers such as phosgene, phosphorus tribromide, phosphorus trichloride, phosphorus pentachloride, phosphorus oxychloride or thionyl chloride may be mentioned as examples; Anhydride formers such as ethyl chloroformate, methyl chloroformate, isopropyl chloroformate, isobutyl chloroformate or methanesulfate fonylchlorid; Carbodiimides, such as N, N'-dicyclohexylcarbodiimide (DCC) or other customary condensing agents, such as phosphorus pentoxide, polyphosphoric acid, N, N'-carbonyldiimidazole, 2-ethoxy-N-ethoxycarbonyl-1,2-dihydroquinoline (EEDQ), triphenylphosphine / tetrachlorocarbon Bromo-tripyrrolidinophosphonium hexafluorophosphate.

Processes (a) and (f) according to the invention are optionally carried out in the presence of a catalyst. Examples include 4-dimethylaminopyridine, 1-hydroxy-benzotriazole or dimethylformamide.

The reaction temperatures can be varied within a substantial range when carrying out processes (a) and (f) according to the invention. In general, temperatures from 0 ° C to 150 ° C, preferably at temperatures from 0 ° C to 80 ° C.

To carry out process (a) according to the invention for the preparation of the compounds of the formula (I), 0.2 to 5 mol, preferably 0.5 to 2 mol, of aniline derivative are generally employed per mol of the carboxylic acid derivative of the formula (H) of the formula (IH).

To carry out process (f) according to the invention for the preparation of the compounds of the formulas (IV) and (V), 0.2 to 5 mol, preferably 0.5 to 2 mol, are generally employed per mol of the carboxylic acid derivative of the formula (H) to alkenaniline of the formula (VTH) or (TX).

Suitable eluents for carrying out process (b) according to the invention are all customary inert, organic solvents and mixtures of these, or else mixtures of these with water. Halogenated aliphatic, alicyclic or aromatic hydrocarbons, such as petroleum ether, hexane, heptane, cyclohexane, can preferably be used; Dichloromethane, chloroform; Alcohols, such as methanol, ethanol, propanol; Nitriles such as acetonitrile; Esters such as methyl acetate or ethyl acetate. It is particularly preferred to use aliphatic hydrocarbons, such as hexane or heptane, and alcohols, such as methanol or propanol, very particularly preferably n-heptane and isopropanol or mixtures of these.

The reaction temperatures can be varied within a substantial range when carrying out process (b) according to the invention. In general, temperatures between 10 ° C and 60 ° C, preferably between 10 ° C and 40 ° C, particularly preferably at room temperature.

When carrying out process (b) according to the invention, an approx Solution of the racemic compound (I-rac) used for the chro atographic separation. However, it is also possible to use other concentrations. The processing takes place according to usual

Methods. In general, the procedure is such that the eluate is largely concentrated, solid

Components filtered off and dried after washing with n-heptane. If necessary, the residue is chromatographically freed from any impurities that may still be present. Mixtures of n-hexane or cyclohexane and ethyl acetate are used as eluents, the composition of which must be adapted to the particular compound to be purified.

Suitable diluents for carrying out the first step of process (d) according to the invention and of process (g) according to the invention are all inert organic solvents. These preferably include nitriles, such as acetonitrile, propionitrile, n- or i-butyronitrile or benzonitrile or amides, such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric acid triamide.

The first step of process (d) according to the invention and process (g) according to the invention are optionally carried out in the presence of a suitable acid acceptor. All conventional inorganic or organic bases are suitable as such. These preferably include alkaline earth metal or alkali metal hydrides, hydroxides, amides, alcoholates, acetates, carbonates or hydrogen carbonates, such as e.g. Sodium hydride, sodium amide, sodium methylate, sodium ethylate, potassium tert-butoxide, sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium acetate, potassium acetate, calcium acetate, ammonium acetate, sodium carbonate, potassium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate or ammonium carbonate, and also tertiary amines, such as Trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, N, N-dimethylbenzylamine, pyridine, N-methylpiperidine, N-methylmorpholine, N, N-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclonones (DBN ) or diazabicycloundecene (DBU).

The first step of process (d) according to the invention and process (g) according to the invention are carried out in the presence of one or more catalysts. Palladium salts or complexes are particularly suitable for this. Palladium chloride, palladium acetate, tetrakis (1riphenylphosphine) palladium or bis (triphenylphosphine) palladium dichloride are preferably used for this purpose. A palladium complex can also be generated in the reaction mixture if a palladium salt and a complex ligand are added separately to the reaction. Organophosphorus compounds are preferred as ligands. Examples include: triphenylphosphine, tri-o-tolylphosphine, 2,2'-bis (diphenylphosphino) -l, r-binaphthyl, dicyclohexylphosphine biphenyl, 1,4-bis (diphenylphosphino) butane, bisdiphenylphosphinoferrocene, di (tert- butylphosphino) biphenyl, di (cyclo- hexylphosphino) biphenyl, 2-dicyclohexylphosphino-2 '-N, N-dimethylaminobiphenyl, tricyclohexylphosphine, tri-tert-butylphosphine. However, ligands can also be dispensed with.

The first step of process (d) according to the invention and process (g) according to the invention are also optionally carried out in the presence of a further metal salt, such as copper salts, for example copper (I) iodide.

When carrying out the first step of process (d) according to the invention and of process (g) according to the invention, the reaction temperatures can be varied within a substantial range. In general, temperatures from 20 ° C to 180 ° C, preferably at temperatures from 50 ° C to 150 ° C.

To carry out the first step of process (d) according to the invention for the preparation of the alkenanilines of the formula (VIH), generally 1 to 5 mol, preferably 1 to 3 mol, of alkene of the formula (1) per mole of the aniline derivative of the formula (VI) VH) a.

To carry out process (g) according to the invention for the preparation of the compounds of the formulas (IV) and (V), 1 to 5 mol, preferably 1 to 3 mol, of alkene of the formula (VH) are generally employed per mol of carboxamide of the formula (X) or (XI).

Suitable diluents for carrying out process (c) according to the invention and the second step (hydrogenation) of process (d) according to the invention are all inert organic solvents. These preferably include aliphatic or alicyclic hydrocarbons, e.g. Petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane or decalin; Ethers, such as diethyl ether, diisopropyl ether, methyl tert-butyl ether, methyl tert-amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane or 1,2-diethoxyethane; Alcohols, such as methanol, ethanol, n- or iso-propanol, n-, iso-, sec- or tert-butanol, ethanediol, propane-1,2-diol, ethoxyethanol, methoxyethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, their mixtures with Water or pure water.

The second step (hydrogenation) of process (d) according to the invention is carried out in the presence of a catalyst. All catalysts which are usually used for hydrogenations are suitable as such. Examples include: Raney nickel, palladium, ruthenium or platinum, optionally on a carrier material, such as e.g. Activated carbon.

The chiral hydrogenation when carrying out process (c) according to the invention and in Process (d) is carried out in the presence of an optically active ligand. They are exemplary

Combination (R, R) -Me-DuPhos / RuCl ₂ ^® or (S, S) -Me-DuPhos / RuCl ₂ ^® (depending on the desired enantiomer).

The hydrogenation in the second step of process (d) according to the invention can also be carried out in the presence of triethylsilane instead of in the presence of hydrogen in combination with a catalyst.

The reaction temperatures can be varied within a substantial range when carrying out process (c) according to the invention and the second step of process (d) according to the invention. In general, temperatures from 0 ° C to 150 ° C, preferably at temperatures from 20 ° C to 100 ° C.

Process (c) according to the invention and the second step of process (d) according to the invention are carried out under a hydrogen pressure between 0.5 and 200 bar, preferably between 2 and 50 bar, particularly preferably between 3 and 10 bar.

Suitable eluents for carrying out the third step of process (d) according to the invention or of process (e) according to the invention are all customary inert, organic solvents and mixtures of these or, if appropriate, mixtures with water. Halogenated aliphatic, alicyclic or aromatic hydrocarbons, such as petroleum ether, hexane, heptane, cyclohexane, can preferably be used; Dichloromethane, chloroform; Alcohols, such as methanol, ethanol, propanol; Nitriles such as acetonitrile; Esters such as methyl acetate or ethyl acetate. It is particularly preferred to use aliphatic hydrocarbons, such as hexane or heptane, and alcohols, such as methanol or propanol, very particularly preferably n-heptane and isopropanol or mixtures of these.

The reaction temperatures can be varied over a wide range when carrying out the third step of process (d) or process (e) according to the invention. In general, temperatures between 10 ° C and 60 ° C, preferably between 10 ° C and 40 ° C, particularly preferably at room temperature.

When the third step of process (d) or process (e) according to the invention is carried out, an approximately 1% strength solution of the racemic compound (IH-a-rac) or (Hl-b-rac) is generally used for the chromatographic separation is used. However, it is also possible to use other concentrations. The processing takes place according to usual Methods. In general, the procedure is such that the eluate is largely concentrated, solid constituents are filtered off and dried after washing with n-heptane. If necessary, the residue is chromatographically freed of any impurities still present. Mixtures of n-hexane or cyclohexane and ethyl acetate are used as eluents, the composition of which must be adapted to the particular compound to be purified.

Unless otherwise stated, all of the processes according to the invention are generally carried out under normal pressure. However, it is also possible to work under increased or reduced pressure - generally between 0.1 bar and 10 bar.

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

Fungicides can be used to protect plants against Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes. Bactericides can be used in crop protection to combat Pseudomonadaceae, Rhizobiaceae, Enterobacteriaceae, Corynebacteriaceae and Streptomycetaceae.

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, e.g. Xanthomonas campestris pv. Oryzae;

Pseudomonas species, e.g. Pseudomonas syringae pv. Lachrymans;

Erwinia species, e.g. Erwinia amylovora; Pythium species, e.g. Pythium ultimum;

Phytophthora species, e.g. Phytophthora infestans;

Pseudoperonospora species, e.g. Pseudoperonospora humuli or

Pseudoperonospora cubensis;

Plasmopara species, e.g. Plasmopara viticola; Bremia species, e.g. Bremia lactucae;

Peronospora species, e.g. Peronospora pisi or P. brassicae;

Erysiphe species, e.g. Erysiphe graminis;

Sphaerotheca species, e.g. Sphaerotheca fuliginea;

Podosphaera species, e.g. Podosphaera leucotricha; Venturia species, such as Venturia inaequalis;

Pyrenophora species, such as, for example, Pyrenophora teres or P. graminea (Conidial form: Drechslera, Syn: Helminthosporium);

Cochliobolus species, e.g. Cochliobolus sativus

(Conidial form: Drechslera, Syn: Helminthosporium);

Uromyces species, e.g. Uromyces appendiculatus; Puccinia species, e.g. Puccinia recondita;

Sclerotinia species, e.g. Sclerotinia sclerotiorum;

Tilletia species, such as Tilletia caries;

Ustilago species, e.g. Ustilago nuda or Ustilago avenae;

Pellicularia species, such as e.g. Pellicularia sasakii; Pyricularia species, e.g. Pyricularia oryzae;

Fusarium species, e.g. Fusarium culmorum;

Botrytis species, e.g. Botrytis cinerea;

Septoria species, e.g. Septoria nodorum;

Leptosphaeria species, e.g. Leptosphaeria nodorum; Cercospora species, e.g. Cercospora canescens;

Alternaria species, e.g. Alternaria brassicae;

Pseudocercosporella species, e.g. Pseudocercosporella herpotrichoides,

Rhizoctonia species, e.g. Rhizoctonia solani.

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

Plant-strengthening (resistance-inducing) substances are to be understood in the present context as substances which are able to stimulate the defense system of plants in such a way that the treated plants develop extensive resistance to these microorganisms when subsequently inoculated with undesired microorganisms.

Undesired microorganisms are to be understood in the present case as phytopathogenic fungi, bacteria and viruses. The substances according to the invention can thus be used to protect plants against attack by the pests mentioned within a certain period of time after the treatment. The period of time within which protection is brought about generally extends from 1 to 10 days, preferably 1 to 7 days, after the treatment of the plants with the active compounds.

The good plant tolerance of the active ingredients in the fight against plant diseases necessary concentrations allow a treatment of above-ground parts of plants, of plant and seed, and the soil.

The active compounds according to the invention can be used with particularly good results in combating cereal diseases, such as e.g. against Puccinia species and diseases in wine, fruit and vegetable growing, e.g. against Botrytis, Venturia or Alternaria species.

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

If appropriate, the active compounds according to the invention can also be used in certain concentrations and application rates as herbicides, for influencing plant growth and for controlling animal pests. If appropriate, they can also be used as intermediates and precursors for the synthesis of further active compounds.

According to the invention, all plants and parts of plants can be treated. Plants are understood here to mean all plants and plant populations, such as desired and undesired wild plants or crop plants (including naturally occurring crop plants). Crop plants can be plants which can be obtained by conventional breeding and optimization methods or by biotechnological and genetic engineering methods or combinations of these methods, including the transgenic plants and including the plant cultivars which can or cannot be protected by plant breeders' rights. Plant parts are to be understood to mean all above-ground and underground parts and organs of the plants, such as shoots, leaves, flowers and roots, examples being leaves, needles, stems, stems, flowers, fruiting bodies, fruits and seeds as well as roots, tubers and rhizomes. The plant parts also include crops and vegetative and generative propagation material, for example cuttings, tubers, rhizomes, offshoots and seeds.

The treatment of the plants and parts of plants with the active compounds according to the invention is carried out directly or by acting on their surroundings, living space or storage space using the customary treatment methods, e.g. by dipping, spraying, vaporizing, atomizing, scattering, spreading and, in the case of propagation material, in particular in the case of seeds, furthermore by coating in one or more layers.

In material protection, the substances according to the invention can be used to protect technical materials against attack and destruction by undesired microorganisms. In the present context, technical materials are understood to mean non-living materials that have been prepared for use in technology. For example, technical materials which are to be protected against microbial change or destruction by active substances according to the invention can be adhesives, glues, paper and cardboard, textiles, leather, wood, paint and plastic articles, cooling lubricants and other materials which can be attacked or decomposed by microorganisms , In the context of the materials to be protected, parts of production systems, for example cooling water circuits, are also mentioned which can be impaired by the multiplication of microorganisms. In the context of the present invention, technical materials are preferably adhesives, glues, papers and cartons, leather, wood, paints, cooling lubricants and heat transfer liquids, particularly preferably wood.

Bacteria, fungi, yeasts, algae and mucilaginous organisms may be mentioned as microorganisms which can cause degradation or a change in the technical materials. The active compounds according to the invention preferably act against fungi, in particular mold, wood-discoloring and wood-destroying fungi (Basidiomycetes) and against slime organisms and algae.

Microorganisms of the following genera may be mentioned, for example:

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.

Depending on their respective physical and or chemical properties, the active ingredients can be converted into the customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, very fine encapsulations in polymeric substances and in coating compositions for seeds, and ULV Cold and warm fog formulations. These formulations are prepared in a known manner, for example by mixing the active ingredients with extenders, that is to say liquid solvents, pressurized liquefied gases and / or solid carriers, optionally using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents. If water is used as an extender, organic solvents can, for example, also be used as auxiliary solvents. The following are essentially suitable as liquid solvents: 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, for example petroleum fractions, alcohols, such as butanol or glycol, and the like 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. Liquefied gaseous extenders or carriers mean those liquids which are gaseous at normal temperature and under normal pressure, for example aerosol propellants such as halogenated hydrocarbons and butane, propane, nitrogen and carbon dioxide. Solid carrier materials come into question: for example natural rock powders such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powders such as highly disperse silica, aluminum oxide and silicates. Solid carriers for granules are possible: e.g. broken and fractionated natural rocks such as calcite, pumice, marble, sepiolite, dolomite as well as synthetic granules from inorganic and organic flours as well as granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stems. Possible emulsifiers and / or foaming agents are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates. Possible dispersants are: eg lignin sulfite waste liquor and methyl cellulose.

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

Dyes such as inorganic pigments, e.g. Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used.

The formulations generally contain between 0.1 and 95 percent by weight of active compound, preferably between 0.5 and 90%. The active compounds according to the invention, as such or in their formulations, can also be used in a mixture with known fungicides, bactericides, acaricides, nematicides or insecticides, in order, for example, to broaden the activity spectrum or to prevent the development of resistance. In many cases, synergistic effects are obtained, ie the effectiveness of the mixture is greater than the effectiveness of the individual components.

The following connections can be considered as mixed partners:

fungicides:

2-Phenylρhenol; 8-hydroxyquinoline sulfate; Acibenzolar-S-methyl; aldimorph; amidoflumet; Ampropylfos; Ampropylfos-potassium; andoprim; anilazine; azaconazole; azoxystrobin; benalaxyl; Benodanil; benomyl; Benthiavalicarb-isopropyl; Benzamacril; Benzamacril-isobutyl; bilanafos; binapacryl;

biphenyl; bitertanol; Blasticidin-S; bromuconazole; Bupirimate; Buthiobate; butylamine; Calcium polysulfides; capsimycin; captafol; captan; carbendazim; carboxin; carpropamid; carvones; Quinomethionate; Chlobenthiazone; Chlorfenazole; chloroneb; chlorothalonil; chlozolinate; Clozylacon; Cyazofamide; cyflufenamid; cymoxanil; cyproconazole; cyprodinil; cyprofuram; DaggerG; debacarb; Dichlorofluanide; dichlone; dichlorophen; diclocymet; Diclomezine; dicloran; diethofencarb; Difenoconazoles; diflumetorim; dimethirimol; dimethomorph; dimoxystrobin; diniconazole; Diniconazole-M;

dinocap; diphenylamines; Dipyrithione; Ditalimfos; dithianon; dodine; Drazoxolon; edifenphos;

epoxiconazole; ethaboxam; ethirimol; etridiazole; famoxadone; fenamidone; Fenapanil; fenarimol; Fenbuconazole; fenfuram; fenhexamid; Fenitropan; fenoxanil; fenpiclonil; fenpropidin; Fenpropimorph; ferbam; fluazinam; Flubenzimine; fludioxonil; flumetover; flumorph; fluoromides; Fluoxastrobin; fluquinconazole; flurprimidol; flusilazole; flusulfamide; flutolanil; flutriafol; folpet; fosetyl

al; Fosetyl-sodium; fuberidazole; furalaxyl; furametpyr; Furcarbanil; Furmecyclox; guazatine;

Hexachlorobenzene; hexaconazole; hymexazol; imazalil; Imibenconazole; Iminoctadine triacetate; Iminoctadine tris (albesilate); lodocarb; ipconazole; iprobenfos; iprodione; iprovalicarb; Irumamycin;

isoprothiolane; Isovaledione; kasugamycin; Kresoxim-methyl; mancozeb; maneb; Meferimzone;

mepanipyrim; mepronil; metalaxyl; Metalaxyl-M; metconazole; methasulfocarb; Methfuroxam;

metiram; metominostrobin; Metsulfovax; mildiomycin; myclobutanil; myclozoline; natamycin;

nicobifen; Nitro Thal-isopropyl; Noviflumuron; nuarimol; ofurace; orysastrobin; oxadixyl; Oxolinic acid; Oxpoconazole; oxycarboxin; Oxyfenthiin; paclobutrazol; Pefurazoate; penconazole; pencycuron;

phosdiphen; phthalides; picoxystrobin; piperalin; Polyoxins; Polyoxorim; Probenazole; prochloraz; Procymidones; propamocarb; Propanosine-sodium; propiconazole; propineb; proquinazid; prothioconazole;

pyraclostrobin; Pyrazohos; pyrifenox; pyrimethanil; pyroquilon; Pyroxyfur; Pyrrolnitrine; Quinconazole; quinoxyfen; quintozene; Simeconazole; Sp oxamine; Sulfur; tebuconazole; tecloftalam; Tecnazene; Tetcyclacis; tetraconazole; thiabendazole; Thicyofen; Thifluzamide; Thiophanate-methyl;

thiram; Tioxymid; Tolclofos-methyl; tolylfluanid; triadimefon; triadimenol; Triazbutil; triazoxide; Tricyclamide; Tricyclazole; tridemorph; trifloxystrobin; triflumizole; triforine; triticonazole; Uniconazole; Validamycin A; vinclozolin; Zineb; ziram; zoxamide; (2S) -N- [2- [4 - [[3- (4-chlorophenyl) -2-propmyl] oxy] -3-memoxyphenyl] el] -3-me l-2 - [(me% isulfonyl) ammo ] butanamide; 1- (1-naphthalenyl) -IH-pyrrole-2,5-dione; 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine; 2-amino-4-methyl-N-phenyl-5-thiazole carboxamide; 2-chloro-N- (2,3-dihydro-l, 1,3-trimemyl-lH-mden-4-yl) -3-pyridinecarboxamide; 3,4,5-trichloro-2,6-pyridinedicarbonitrile; Actinovate; cis-1- (4-chlorophenyl) -2- (1H-1,2,4-triazol-1-yl) cycloheptanol; Methyl l- (2,3-dihydro-2,2-dimemyl-lH-mden-l-yl) -IH-irididazole-5-carboxylate; Mono potassium carbonate; N- (6-methoxy-3-pyridinyl) -cyclopropanecarboxamide; N-butyl-8- (l, l-dimethylethyl) -l-oxaspiro [4.5] decan-3-amine; sodium tetrathiocarbonate; as well as copper salts and preparations, such as Bordeaux mixture; copper; naphthenate; copper oxychloride; Copper sulfate; Cufraneb; copper; mancopper; Oxine-copper.

bactericides:

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

Insecticides / acaricides / nematicides:

1. Acetylcholinesterase (AChE) inhibitors 1.1 carbamates (for example alanycarb, aldicarb, aldoxycarb, Allyxycarb, aminocarb, azamethiphos, benzyl diocarb, Benfüracarb, Bufencarb, Butacarb, Butocarboxim, Butoxycarboxim, carbaryl, carbofuran, carbosulfan, Chloethocarb, coumaphos, Cyanofenphos, Cyanophos , Dimetilan, Ethiofencarb, Fenobarb, Fenothiocarb, Formetanate, Furathiocarb, Isoprocarb, Metam-sodium, Methiocarb, Methomyl, Metolcarb, Oxamyl, Pirimicarb, Promecarb, Propoxur, Thiodicarb, Thiofanox, Triazamate, Tri ethacarbylCarb

1.2 Organophosphates (e.g. acephate, azamethiphos, azinphos (-methyl, -ethyl), bromophos-ethyl, bromfenvinfos (-methyl), butathiofos, cadusafos, carbophenothion, chlorethoxyfos, chlorfenvinphos, chlormephos, chlorpyrifos (-maphos-ethyl) , Cyanofenphos, Cyanophos, Chlorfenvinphos, Demeton-S-methyl, Demeton-S-methylsulphon, Dialifos, Diazinon, Dichlofenthion, Dichlorvos / DDVP, Dicrotophos, Dimethoate, Dimethylvinphos, Dioxabenzofos, Disulfoton, EPN, Ethi- on , Etrimfos, Famphur, Fenamiphos, Fenitrothion, Fensulfothion, Fenthion, Flupyrazo- fos, Fonofos, Formothion, Fosmethilan, Fosthiazate, Heptenophos, Iodofenphos, Iprobefos, Isazofos, Isofenphos, Isopropyl Iso, Methathionos, Malafion, Methacionate, Methacionate, Methacionate, Methacionate, Methacionate, Methacionate, Methacionate, Methacionate Methamidophos, Methidathion, Mevinphos, Monocrotophos, Naled, Omethoate, Oxydemeton-methyl, Parathion (-methyl / -ethyl), Phenthoate, Phorate, Phosalone, Phosmet, Phosphamidon, Phosphocarb, Phoxim, Pirimiphos (-methyl / -ethyl), Profenofos, Propapho s, Propetamphos, Prothiofos, Prothoate, Pyraclo- fos, pyridaphenthion, pyridathion, quinalphos, sebufos, sulfotep, sulprofos, tebupirimfos,

Temephos, Terbufos, Tetrachlorvinphos, Thiometon, Triazophos, Triclorfon, Vamidothion)

2. Sodium channel modulators / voltage-dependent sodium channel blockers

2.1 Pyrethroids (e.g. acrinathrin, allethrin (d-cis-trans, d-trans), beta-cyfluthrin, bifenthrin, bioallethrin, bioallethrin-S-cyclopentyl isomer, bioemanomethrin, biopermethrin, bioresmethrin, chlova-porthrin, cis , Cis-resmethrin, cis-permethrin, clocythrin, cycloprothrin, cyfluthrin, cyhalothrin, cypermethrin (alpha, beta, theta, zeta), cyphenothrin, DDT, deltamethrin, empenetrin (lR-isomer), esfenproxerate , Fenfluthrin, Fenpropathrin, Fenpyrithrin, Fenvalerate, Flubrocythrinate, Flucythrinate, Flufenprox, Flumethrin, Fluvalinate, Fubfenprox, Gamma-Cyhalothrin, Imiprothrin, Kadethrin, Lambda-Cyhalothrin (Permithrin), Metofethrin (Metoflhrin) lR-trans isomer), Prallethrin, Profluthrin, Protrifenbute, Pyresmethrin, Resmethrin, RU 15525, Silafluofen, Tau-Fluvalinate, Tefluthrin, Terallethrin, Tetramethrin (lR-Isomer), Tralomethrin, Transflutinshrin, PyrXhrhrin, PyrX

2.2 Oxadiazines (e.g. indoxacarb) 3. Acetylcholine receptor agonist antagonists

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

3.2 Nicotine, Bensultap, Cartap

4.Acetylcholine receptor modulators 4.1 spinosyns (e.g. spinosad)

5. GABA-gated chloride channel antagonists

5.1 Cyclodienes Organochlorine (e.g. Camphechlor, Chlordane, Endosulfan, Gamma-HCH, HCH, Heptachlor, Lindane, Methoxychlor

5.2 Fiprole (e.g. Acetoprole, Ethiprole, Fipronil, Vaniliprole) 6. Chloride channel activators

6.1 Mectins (e.g. abamectin, avermectin, emamectin, emamectin-benzoate, ivermectin, mitemectin, milbemycin)

7. Juvenile hormone mimetics

(e.g. Diofenolan, Epofenonane, Fenoxycarb, Hydroprene, Kinoprene, Methoprene, Pyriproxifen, Triprene)

8. Ecdysonagonists / disruptors

8.1 Diacylhydrazine (e.g. chromafenozide, halofenozide, methoxyfenozide, tebufenozide)

9. Inhibitors of chitin biosynthesis

9.1 Benzoyl ureas (e.g. bistrifluron, chlofluazuron, diflubenzuron, fluazuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, penfluron, teflubenzuron, tri-flumuron) 9.2 Buprofezin

9.3 Cyromazines

10.Inhibitors of oxidative phosphorylation, ATP disruptors 10.1 diafenthiuron 10.2 organotins (e.g. azocyclotin, cyhexatin, fenbutatin-oxide)

11. Decoupler of oxidative phosphorylation by interrupting the H proton gradient

11.1 pyrroles (e.g. chlorfenapyr)

11.2 Dinitrophenols (e.g. Binapacyrl, Dinobuton, Dinocap, DNOC)

12.Side-I electron transport inhibitors 12.1 METI's (e.g. fenazaquin, fenpyroximate, pyrimidifen, pyridaben, tebufenpyrad, tolfenpyrad)

12.2 Hydramethylnone

12.3 Dicofol

13. Side-II electron transport inhibitors 13.1 Rotenones 14. Side-III electron transport inhibitors

14.1 acequinocyl, fluacrypyrim

15. Microbial disruptors of the insect intestinal membrane strains of Bacillus thuringiensis

16. Inhibitors of fat synthesis 16.1 tetronic acids (e.g. spirodiclofen, spiromesifen)

16.2 tetramic acids [e.g. 3- (2,5-Dimethylphenyl) -8-methoxy-2-oxo-l-azaspiro [4.5] dec-3-en-4-yl ethyl carbonate (alias: Carbonic acid, 3- (2,5-dimethylphenyl) -8-methoxy-2-oxo-l-azaspiro [4.5] dec-3-en-4-yl ethyl ester, CAS Reg.-No .: 382608-10-8) and Carbonic acid, cis-3- ( 2,5-dimethylphenyl) -8-methoxy-2-oxo-l-azaspiro [4.5] dec-3-en-4-yl ethyl ester (CAS Reg.No .: 203313-25-1)] 17. Carboxamides (e.g. flonicamide)

18. Octopaminergic agonists (e.g. Amitraz)

19.Inhibitors of magnesium-stimulated ATPase (e.g. propargite)

20. Phthalamides

(e.g. N ² - [l, l-dimemyl-2- (methylsulfonyl) el] -3-iodo-N ^, - [2-me l-4- [l, 2,2,2-tetrafluoro-l- (trifluor - me l) ethyl] phenyl] -l, 2-benzenedicarboxamide (CAS Reg.-No .: 272451-65-7))

21.Nereistoxin analogs (e.g. Thiocyclam hydrogen oxalate, Thiosultap-sodiurn)

22. Biologicals, hormones or pheromones (e.g. Azadirachtin, Bacillus spec, Beauveria spec, Codlemone, Metarrhician spec, Paecilomyces spec, Thuringiensin, Verticillium spec.)

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

23.1 Fumigants (e.g. aluminum phosphide, methyl bromide, sulfuryl fluoride) 23.2 Selective feeding inhibitors (e.g. cryolite, flonicamide, pymetrozine)

23.3 mite growth inhibitors (e.g. clofentezine, etoxazole, hexythiazox)

23.4 Amidoflumet, Benclothiaz, Benzoximate, Bifenazate, Bromopropylate, Buprofezin, Chinomethionate, Chlordimeform, Chlorobenzilate, Chloropicrin, Clothiazoben, Cycloprene, Dicyclanil, Fenoxa- crim, Fentrifanil, Flubenzimine, Flufenerimaponone, Flufenerimaponone, Flufenerimaponone, Flufenerimaponone, Flufenerimaponone, Flufenerimaponone, Flufenerimaponone, Flufenerimaponone, Flufenerimaponone, Flufenerimaponone, Flufenerimaponone, Flufenerimaponone, Flufenerimaponone, Flufenerimaponone, Flufenerimaponone, Flufenerimaponone, Flufenerimaponone, Flufenerimaponone, Flufenerimaponone , Piperonyl butoxide, Potassium oleate, Pyridalyl, Sulfluramid, Tetradifon, Tetrasul, Triarathene, Verbutin

furthermore the compound 3-methyl-phenyl-propylcarbamate (Tsumacide Z), the compound 3- (5-chloro-3-pyridinyl) -8- (2,2,2-trifluoroethyl) -8-azabicyclo [3.2.1] octane -3-carbonitrile (CAS Reg.No. 185982-80- 3) and the corresponding 3-endo isomer (CAS Reg.No. 185984-60-5) (cf. WO-96/37494, WO - 98/25923), and preparations which contain insecticidally active plant extracts, nematodes, fungi or viruses.

A mixture with other known active compounds, such as herbicides or with fertilizers and growth regulators, safeners or semiochemicals, is also possible.

In addition, the compounds of the formula (I) according to the invention also have very good antimycotic effects. They have a very broad spectrum of antifungal effects, in particular against dermatophytes and shoot fungi, mold and diphasic fungi (e.g. against Candida species such as Candida albicans, Candida glabrata) as well as Epidermophyton floccosum, Aspergillus species such as Aspergillus niger and Aspergillophytonophytonyspecytonyspecyspecific trichomes mentagrophytes, microsporon species such as microsporon canis and audouinii. The list of these fungi is in no way a limitation of the detectable mycotic spectrum, but is only of an explanatory nature.

The active compounds can be used as such, in the form of their formulations or the use forms prepared therefrom, such as ready-to-use solutions, suspensions, wettable powders, pastes, soluble powders, dusts and granules. They are used in the customary manner, for example by watering, spraying, atomizing, scattering, dusting, foaming, brushing, etc. It is also possible to apply the active ingredients by the ultra-low-volume process or to prepare the active ingredient or the active ingredient itself Inject soil. It can also be the seed of the plants are treated.

When the active compounds according to the invention are used as fungicides, the application rates can be varied within a relatively wide range, depending on the type of application. In the treatment of parts of plants, the active compound application rates are generally between 0.1 and 10,000 g / ha, preferably between 10 and 1,000 gha. 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 soil, the active compound application rates are generally between 0.1 and 10,000 g / ha, preferably between 1 and 5,000 g / ha.

As already mentioned above, according to the invention, all plants and their parts can be treated. In a preferred embodiment, plant species and plant varieties and their parts occurring wildly or obtained by conventional biological breeding methods, such as crossing or protoplast fusion, are treated. In a further preferred embodiment, transgenic plants and plant cultivars which have been obtained by genetic engineering methods, if appropriate in combination with conventional methods (genetically modified organisms) and their parts are treated. The term “parts” or “parts of plants” or “parts of plants” was explained above.

Plants of the plant varieties which are in each case commercially available or in use are particularly preferably treated according to the invention. Plant cultivars are understood to mean plants with new properties (“traits”) which have been cultivated by conventional breeding, by mutagenesis or by recombinant DNA techniques. These can be cultivars, breeds, bio- and genotypes.

Depending on the plant species or plant cultivars, their location and growth conditions (soils, climate, vegetation period, nutrition), the treatment according to the invention can also cause superadditive (“synergistic”) effects. For example, reduced application rates and / or widening of the activity spectrum and / or one Enhancing the effect of the substances and agents which can be used according to the invention, better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to water or soil salt content, increased flowering performance, easier harvesting, acceleration of ripeness, higher crop yields, higher quality and / or higher Nutritional value of the crop products, higher shelf life and / or workability of the crop products possible, which go beyond the effects that are actually to be expected. The preferred transgenic plants or plant cultivars to be treated according to the invention include all plants which have received genetic material through the genetic engineering modification, which gives these plants particularly advantageous valuable properties (“traits”). Examples of such properties are better plant growth, Increased tolerance to high or low temperatures, increased tolerance to drought or to water or soil salt content, increased flowering performance, easier harvesting, acceleration of ripeness, higher harvest yields, higher quality and / or higher nutritional value of the harvest products, longer shelf life and / or Processability of the crop products Further and particularly highlighted examples of such properties are an increased defense of the plants against animal and microbial pests, such as against insects, mites, phytopathogenic fungi, bacteria and / or vire n and an increased tolerance of the plants to certain herbicidal active ingredients. Examples of transgenic plants are the important crop plants, such as cereals (wheat, rice), corn, soybeans, potatoes, cotton, tobacco, rapeseed and fruit plants (with the fruits apples, pears, citrus fruits and grapes), with corn, soybeans, potatoes , Cotton, tobacco and rapeseed. The properties (“traits”) which are particularly emphasized are the plants' increased defense against insects, arachnids, nematodes and snails due to toxins which arise in the plants, in particular those which are caused by the genetic material from Bacillus thuringiensis (for example by the genes CryIA (a) , CryIA (b), CryΙA (c), CryHA, CryHIA, CryIHB2, Cry9c Cry2Ab, Cry3Bb and CrylF as well as their combinations) are produced in the plants (hereinafter, "plants"). The increased defense of plants against fungi, bacteria and viruses by systemic acquired resistance (SAR), systemin, phytotoxins, elicitors and resistance genes and correspondingly expressed proteins and toxins are also particularly emphasized as traits. Traits ") are also particularly emphasized the increased tolerance of the plants to certain herbicidal active ingredients, for example imidazolinones, sulfonylureas, glyphosate or phosphinotricin (for example" PAT "gene). The genes imparting the desired properties (“traits”) can also be found in combinations with one another in the transgenic plants. Examples of “Bt plants” are corn varieties, cotton varieties, soy varieties and potato varieties that are marketed under the trade names YTJELD GARD® (eg corn , Cotton, soy), KnockOut® (e.g. maize), StarLink® (e.g. maize), Bollgard® (cotton), Nucoton® (cotton) and NewLeaf® (potato). Examples of herbicide-tolerant plants are corn varieties, cotton varieties and soy varieties that are sold under the trade names Roundup Ready® (tolerance to glyphosate e.g. corn, cotton, soy), Liberty Link® (tolerance to phosphinotricin, e.g. rapeseed), HVH® (tolerance to Imidazolinone) and STS® (tolerance to sulfonylureas such as maize). The herbicide-resistant plants (conventionally bred to herbicide tolerance) include the varieties marketed under the name Clearfϊeld® (eg maize). Selbstver- Of course, these statements also apply to plant varieties developed in the future or coming onto the market in the future with these or future-developed genetic properties ("traits").

The plants listed can be treated particularly advantageously according to the invention with the compounds of the general formula (I) or the active compound mixtures according to the invention. The preferred ranges given above for the active substances or mixtures also apply to the treatment of these plants. Plant treatment with the compounds or mixtures specifically listed in the present text should be particularly emphasized.

The preparation and use of the active compounds according to the invention can be seen from the following examples.

Preparation Examples

example 1

(+/-) - N- [2- (1,3-dimethylbutyl) phenyl] -5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide (200 mg) is dissolved in 25 ml n-heptane / Isopropanol 9: 1 (v / v = volume / volume) dissolved. The solution is then chromatographed on the Chiralcel OD ^® silica gel phase [manufacturer: Daicel (Japan), column dimension: 500 mm × 40 mm (ID), particle size: 20 μm, flow rate: 40 ml / min] with n-heptane / Isopropanol 9: 1 (v / v) as an eluent according to the principle of high performance liquid chromatography (HPLC). To separate the entire amount, 5 ml (corresponding to 40 mg of the racemate) are applied to the column every 30 minutes. The compounds are detected with a UV detector at a wavelength of 210 nm. After analysis of the enantiomeric purity, the eluate fractions are pooled accordingly, largely evaporated in vacuo, the residues are filtered off and dried after washing with n-heptane. The crude product thus obtained is purified on silica gel (mobile phase: n-hexane / ethyl acetate, 1: 9 → 1: 4, in each case v / v).

87 mg of N- {2 - [(IS) -1,3-dimethylbutyl] phenyl} -5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide (melting point 52-54 ° C. , Rotation value [α] _D = +6.7, c = 0.87; methanol, 20 ° C, ee value = 99%).

The enantiomeric purity of the carboxamides of the formula (I) was determined by means of analytical HPLC under the following conditions:

Separation phase: Chiralcel OD (Daicel, Japan); 5 μm column: 250 mm x 4.6 mm (I.D.)

Eluent: n-heptane / 2-propanol 10: 1

Flow rate: 0.5 ml / min

UV detection: 210 nm

Analogously to Example 1, and in accordance with the information in the general process descriptions, the compounds of the formula (I) mentioned in Table 1 below are obtained. Table 1

The logP values specified in the tables and manufacturing examples above are determined in accordance with EEC Directive 79/831 Annex V.A8 by HPLC (High Performance Liquid Chromatography) on a phase reversal column (C 18). 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. The calibration is carried out with unbranched alkan-2-ones (with 3 to 16 carbon atoms) whose logP values are known (determination of the logP values on the basis of the retention times by linear interpolation between two successive alkanones).

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

Example A

Podosphaera test (apple) / protective

Solvent: 24.5 parts by weight of acetone 24.5 parts by weight of dimethylacetamide emulsifier: 1 part by weight of alkyl aryl polyglycol ether

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

To test for protective activity, young plants are sprayed with the preparation of active compound in the stated application rate. After the spray coating has dried on, the plants are inoculated with an aqueous spore suspension of the pod mildew pathogen Podosphaera leucotricha. The plants are then placed in the greenhouse at about 23 ° C. and a relative humidity of about 70%.

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

Table A Podosphaera test (apple) / protective According to the invention:

Comparison Test:

According to the invention:

Comparison Test:

Example B

Sphaerotheca test (cucumber) / protective

Solvent: 24.5 parts by weight of acetone 24.5 parts by weight of dimethylacetamide emulsifier: 1 part by weight of alkylaryl polyglycol ether

To test for protective efficacy, young cucumber plants are sprayed with the active compound preparation in the stated application rate. After the spray coating has dried on, the plants are inoculated with an aqueous spore suspension of Sphaerotheca fuliginea. The plants are then placed in the greenhouse at about 23 ° C. and a relative atmospheric humidity of about 70%.

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

Table B Sphaerotheca test (cucumber) / protective According to the invention:

Comparison Test:

According to the invention:

Comparison Test:

Table B Sphaerotheca test (cucumber) / protective According to the invention:

Comparison Test:

Erfmdungsgemäß:

Comparison Test:

Table B Sphaerotheca test (cucumber) / protective According to the invention:

Comparison Test:

Example C

Venturia test (apple) / protective

To test for protective activity, young plants are sprayed with the preparation of active compound in the stated application rate. After the spray coating has dried on, the plants are inoculated with an aqueous conidia suspension of the Venturia inaequalis apple scab pathogen and then remain in an incubation cabin at about 20 ° C. and 100% relative atmospheric humidity for 1 day.

The plants are then placed in the greenhouse at approximately 21.degree. C. and a relative atmospheric humidity of approximately 90%.

Table C Venturia test (apple) / protective According to the invention:

Comparison Test:

Erfmdungsgemäß:

Comparison Test:

Table C Venturia test (apple) / protective According to the invention:

Comparison Test:

According to the invention:

Comparison Test:

Table C Venturia test (apple) / protective According to the invention:

Comparison Test:

According to the invention:

Comparison Test:

Example D

Botrytis test (bean) / protective

To test for protective activity, young plants are sprayed with the preparation of active compound in the stated application rate. After the spray coating has dried on, 2 small pieces of agar covered with botrytis cinerea are placed on each leaf. The inoculated plants are placed in a darkened chamber at approx. 20 ° C and 100% relative humidity.

2 days after the inoculation, the size of the infection spots on the leaves is evaluated. 0% means an efficiency that corresponds to that of the control, while an efficiency of 100% means that no infection is observed.

Table D Botrytis test (bean) / protective According to the invention:

Comparison Test:

According to the invention:

Comparison Test:

Table D Botrytis test (bean) / protective According to the invention:

Comparison Test:

Erfϊndungsgemäß:

Comparison Test:

Table D Botrytis test (bean) / protective According to the invention:

Comparison Test:

Example E

Alternaria test (tomato) / protective

To test for protective activity, young plants are sprayed with the preparation of active compound in the stated application rate. After the spray coating has dried on, the plants are inoculated with an aqueous spore suspension of Altemaria solani. The plants are then placed in an incubation cabin at approx. 20 ° C and 100% relative humidity.

Evaluation is carried out 3 days after the inoculation. 0% means an efficiency that corresponds to that of the control, while an efficiency of 100% means that no infection is observed.

Table E Alternaria test (tomato) / protective According to the invention:

Comparison Test:

Claims

claims

1. Optically active carboxamides of the formula (I)

in which R represents hydrogen, fluorine, chlorine, methyl, ethyl or trifluoromethyl,

M ^{stands for} _' Ml M-2 M-3 M-4 where the bond marked with * is linked to the amide, while the bond marked with # is linked to the alkyl side chain, R ^{1 represents} hydrogen, fluorine, chlorine, methyl or trifluoromethyl,

A for the rest of the formula (AI)

(AI) is in which R ^{2 represents} methyl, trifluoromethyl or difluoromethyl, R ^{3 represents} hydrogen, fluorine or chlorine, or A represents the rest of the formula (A2)

(A2) stands in which R ^{4 represents} trifluoromethyl, chlorine, bromine or iodine, or A represents the rest of the formula (A3)

(A3) stands in which R> 5 represents methyl, trifluoromethyl or difluoromethyl.

2. Optically active carboxamides of the formula (I) according to Claim 1, in which R is hydrogen, methyl or ethyl, M is Ml or M-2, R ^{1 is} hydrogen, fluorine, chlorine, methyl or trifluoromethyl, R ² represents methyl or trifluoromethyl, R ^{3 represents} hydrogen or fluorine, R ^{4 represents} trifluoromethyl or iodine, R ^{5 represents} trifluoromethyl.

3. A process for the preparation of optically active carboxamides of the formula (I) according to Claim 1, characterized in that a) carboxylic acid derivatives of the formula (H) O _A ^ _X ¹ π ⁾ in which A has the meanings given in Claim 1 and X ^{1 represents} halogen or hydroxy, with an amine of the formula (JE)

in which R and M have the meanings given in Claim 1, if appropriate in the presence of a catalyst, if appropriate in the presence of a condensing agent, if appropriate in the presence of an acid binder and if appropriate in the presence of a diluent, or b) racemic compounds of the formula (I-rac)

in which R, M and A have the meanings given in Claim 1, chromatographed on a chiral stationary silica gel phase in the presence of an eluent or an eluent mixture as the liquid phase, or fractionally crystallizes with optically active acids with salt formation and then the enantiomerically pure or releases enriched compounds of formula (I), or c) compounds of the formula (TV)

in which R, M and A have the meanings given in spoke 1, or compounds of the formula (V)

in which R, M and A have the meanings given in claim 1, or mixtures of both compounds in the presence of an optically active catalyst or a catalyst with optically active ligand.

Agents for controlling undesired microorganisms, characterized by a content of at least one optically active carboxamide of the formula (I) according to Claim 1, in addition to extenders and / or surface-active substances.

5. Use of optically active carboxamides of the formula (I) according to spoke 1 for combating undesirable microorganisms.

6. A method for controlling unwanted microorganisms, characterized in that optically active carboxamides of the formula (I) according to claim 1 are applied to the microorganisms and / or their habitat.

7. A process for the preparation of agents for controlling unwanted microorganisms, characterized in that optically active carboxamides of the formula (I) according to Claim 1 are mixed with extenders and / or surface-active substances.

Amines of the formula (JE)

in which R and M have the meanings given in spoke 1.