DE102004005317A1 - Optically active carboxamides - Google Patents

Abstract

New optically active carboxamides of the formula (I), in which R, M and A have the meanings given in the description, DOLLAR A several processes for preparing these substances and their use for controlling unwanted microorganisms and new intermediates and their preparation.

Description

The The present invention relates to novel optically active carboxamides, Several processes for their preparation and their use for fight of unwanted Microorganisms.

It It is already known that numerous carboxamides have fungicidal properties (see for example WO 03/010149, WO 02/059086, WO 02/38542, WO 00/09482, DE-A 102 29 595, EP-A 0 591 699, EP-A 0 589 301 and EP-A 0 545 099). Thus, e.g. the racemates of 5-fluoro-1,3-dimethyl-N- [2- (1,3,3-trimethylbutyl) phenyl] -1H-pyrazole-4-carboxamide from WO 03/010149 and N- [2- (1,3-dimethylbutyl) phenyl] -2-iodobenzamide known from DE-A 102 29 595. The effectiveness of these substances is good, but lets at low application rates in some cases to be desired.

Because of the diverse Requirements for modern pesticides, for example, what effective height, Duration of action, spectrum of action, spectrum of application, toxicity, combination with other active ingredients, combination with formulation aids or the synthesis, and the possible occurrence of resistance However, the development of such substances can never be completed and there is a constant need for new ones Compounds that, at least in some aspects, have advantages over the bring known compounds.

gefunden, in welcher
R für Wasserstoff, Fluor, Chlor, Methyl, Ethyl oder Trifluormethyl steht,

wobei die mit * markierte Bindung mit dem Amid verbunden ist, während die mit # markierte Bindung mit der Alkylseitenkette verknüpft ist,
R¹ für Wasserstoff, Fluor, Chlor, Methyl oder Trifluormethyl steht,
A für den Rest der Formel (A1)

R² für Methyl, Trifluormethyl oder Difluormethyl steht,
R³ für Wasserstoff, Fluor oder Chlor steht, oder
A für den Rest der Formel (A2)

R⁴ für Trifluormethyl, Chlor, Brom oder Iod steht, oder
A für den Rest der Formel (A3)

R⁵ für Methyl, Trifluormethyl oder Difluormethyl steht.There have now been new optically active carboxamides of the formula (I)

found in which
R is hydrogen, fluorine, chlorine, methyl, ethyl or trifluoromethyl,

wherein the bond marked with * is linked to the amide, while the bond marked # is linked to the alkyl side chain,
R ^{1 is} hydrogen, fluorine, chlorine, methyl or trifluoromethyl,
A for the rest of the formula (A1)

R ^{2 is} methyl, trifluoromethyl or difluoromethyl,
R ^{3 is} hydrogen, fluorine or chlorine, or
A is the radical of the formula (A2)

R ^{4 is} trifluoromethyl, chlorine, bromine or iodine, or
A for the rest of the formula (A3)

R ^{5 is} methyl, trifluoromethyl or difluoromethyl.

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

• a) Carbonsäure-Derivate der Formel (II)
  
  in welcher A die oben angegebenen Bedeutungen hat und X¹ für Halogen oder Hydroxy steht, mit einem Amin der Formel (III)
  
  in welcher R und M die oben angegebenen Bedeutungen haben, gegebenenfalls in Gegenwart eines Katalysators, gegebenenfalls in Gegenwart eines Kondensationsmittels, gegebenenfalls in Gegenwart eines Säurebindemittels und gegebenenfalls in Gegenwart eines Verdünnungsmittels umsetzt, oder
• b) racemische Verbindungen der Formel (I-rac)
  
  in welcher R, M und A die oben angegebenen Bedeutungen haben, an einer chiralen stationären Kieselgelphase in Gegenwart eines Eluenten oder eines Eluenten-Gemisches als flüssiger Phase chromatographiert, oder mit optisch aktiven Säuren unter Salzbildung fraktioniert kristallisiert und anschließend die enantiomerenreine oder angereicherte Verbindung der Formel (I) freisetzt, oder
• c) Verbindungen der Formel (IV)
  
  in welcher R, M und A die oben angegebenen Bedeutungen haben, oder Verbindungen der Formel (I)
  
  in welcher R, M und A die oben angegebenen Bedeutungen haben, oder Gemische beider Verbindungen in Gegenwart eines optisch aktiven Katalysators bzw. eines Katalysators mit optisch aktivem Liganden hydriert.

It has furthermore been found that optically active carboxamides of the formula (I) are obtained by reacting

• a) carboxylic acid derivatives of the formula (II)
  
  in which A has the meanings given above and X ^{1 is} halogen or hydroxyl, with an amine of the formula (III)
  
  in which R and M have the abovementioned meanings, 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 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 compound 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 (I)
  
  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 hydrogenated.

Finally became found that the new optically active carboxamides of the formula (I) have very good microbicidal properties and to combat unwanted Microorganisms both in crop protection and in the protection of materials are usable.

The new optically active carboxamides of the formula (I) are distinguished from known Carboxamides especially by improved effect, or lower Application rate and thus lower environmental impact and reduced toxicity out.

The according to the invention optical Active carboxamides are generally defined by the formula (I). Preferred radical definitions of the above and below Formulas are given below. These definitions apply to the final products of the formula (I) as for all intermediates alike.

R is preferably for Hydrogen, methyl or ethyl.

R is particularly preferred for Hydrogen or methyl.

M is preferably for M -1.

M is also available preferred for M-2.

M is also available preferred for M-third

M is also available preferred for M-4th

M is particularly preferably M-1, wherein R ^{1 is} hydrogen.

M is also more preferably M-2, wherein R ^{1 is} hydrogen.

R ¹ is preferably hydrogen.

R ¹ furthermore preferably represents fluorine, with 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 radical [cf. above formula (I)].

A is preferably for the rest of A1.

A is particularly preferred for A1 meaning 5-fluoro-1,3-dimethyl-1H-pyrazol-4-yl, 3-trifluoromethyl-1-methyl-1H-pyrazol-4-yl or 3-difluoromethyl-1-methyl-1H-pyrazol-4-yl.

A is very particularly preferred for A1 meaning 5-fluoro-1,3-dimethyl-1H-pyrazol-4-yl.

A is also available preferred for the rest A2.

A is particularly preferred for A2 meaning 2-trifluoromethylphenyl or 2-iodo-phenyl.

A is also available preferred for the rest A3.

A is particularly preferred for A3 meaning 1,4-dimethylpyrazol-3-yl, 1-methyl-4-trifluoromethyl-pyrazol-3-yl or 1-methyl-4-difluoromethyl-pyrazol-3-yl.

A is very particularly preferred for A3 meaning 1-methyl-4-trifluoromethyl-pyrazol-3-yl.

R ² is preferably methyl or trifluoromethyl.

R ³ is preferably hydrogen or fluorine.

R ⁴ is preferably trifluoromethyl or iodine.

R ⁵ is preferably trifluoromethyl.

However, the general or preferred radical definitions or explanations given above can also be combined with one another as desired, ie between the respective ranges and preferred ranges. They apply to the end products as well as to the precursors and intermediates speaking.

The mentioned definitions be combined with each other in any way. Besides, too individual definitions are omitted.

Prefers, particularly preferred or most preferred are compounds of the formula (I), each of which is preferred among, particularly preferred or very particularly preferably mentioned substituents.

Explanation of processes and intermediates

Method (a)

If 1-methyl-4- (trifluoromethyl) -1H-pyrrole-3-carbonyl chloride and {2 - [(1S) -1,3,3-trimethylbutyl] -phenyl} amine are used as starting materials, the process according to the invention ( a) are illustrated by the following formula scheme:

The carboxylic acid derivatives required as starting materials for carrying out the process (a) according to the invention are generally defined by the formula (II). In this formula (II) A has preferably, more preferably or very particularly preferably those meanings which have already been indicated in connection with the description of the compounds of the formula (I) according to the invention as being preferred, particularly preferred or very particularly preferred for A. X ¹ is preferably chlorine, bromine or hydroxyl, more preferably chlorine.

The Carboxylic acid derivatives of the formula (II) are known (cf., WO 93/11117, EP-A 0 545 099, US Pat. EP-A 0 589 301 and EP-A 0 589 313).

The to carry out the method according to the invention (a) Amines which are still required as starting materials are Formula (III) generally defined. In this formula (III), R and M is preferred, more preferably or very particularly preferred those meanings that are already related to the description the compounds of the invention of the formula (I) for these radicals are preferred, particularly preferred or very particular were preferred.

The Amines of the formula (III) are new.

in welcher
R die oben angegebenen Bedeutungen hat,
M¹ für M-1 steht,
lassen sich beispielsweise herstellen, indem man

• d) in einem ersten Schritt ein Anilin-Derivat der Formel (VI)
  
  in welcher R¹ die oben angegebenen Bedeutungen hat, mit einem Alken der Formel (VII)
  
  in welcher R die oben angegebenen Bedeutungen hat, in Gegenwart eines Katalysators, gegebenenfalls in Gegenwart einer Base und gegebenenfalls in Gegenwart eines Verdünnungsmittels umsetzt, und das so erhaltene Alkenanilin der Formel (VIII)
  
  in welcher R und R¹ die oben angegebenen Bedeutungen haben, in einem zweiten Schritt gegebenenfalls in Gegenwart eines Verdünnungsmittels und gegebenenfalls in Gegenwart eines Katalysators hydriert, und das so erhaltene racemische Anilin-Derivat der Formel (III-a-rac)
  
  in welcher R und R¹ die oben angegebenen Bedeutungen haben, in einem dritten Schritt an einer chiralen stationären Kieselgelphase in Gegenwart eines Eluenten oder eines Eluenten-Gemisches als flüssiger Phase chromatographiert.

Amines of the formula (III-a)

in which
R has the meanings given above,
M ^{1 stands} for M-1,
can be produced, 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 (VII)
  
  in which R has the abovementioned meanings, 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 alkeneaniline of the formula (VIII) thus obtained
  
  in which R and R ^{1 have} the abovementioned meanings, in a second step if appropriate hydrogenated in the presence of a diluent and if appropriate in the presence of a catalyst, and the resulting racemic aniline derivative of the formula (III-a-rac)
  
  in which R and R ^{1 have} the meanings given above, chromatographed in a third step 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 formula (VIII) may optionally also in the presence of an optically active catalyst, or in the presence a catalyst and an optically active ligand, and Thus, optically active compounds of the formula (III-a) ran.

links of the formula (III-a-rac) also fractionated in the presence of optically active acids with salt formation be crystallized, after which enantiomerically pure or enriched Release compound of formula (III-a). As acids to form diastereomeric Salts are generally suitable for all optically active acids. exemplary may be mentioned: (1S) - (+) - 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, preferred of course occurring optically active amino acids.

The aniline derivatives required as starting materials for carrying out the process (d) according to the invention are generally defined by the formula (VI). In this formula (VI) R ¹ is preferred, particularly preferred or very particularly preferred meanings as preferred in connection with the description of the compounds of formula (I) according to the invention for these radicals, particularly preferred and very particularly preferred, were.

Aniline derivatives of the formula (VI) are known.

The to carry out the method according to the invention (d) Alkenes which are still required as starting materials are characterized by Formula (VII) generally defined. In this formula (VII), R has preferred particularly preferably or very particularly preferably those meanings already in connection with the description of the compounds of the invention of the formula (I) for this radical as preferred, particularly preferred or very particular were preferred.

alkenes of the formula (VII) are known or can be prepared by known methods to be obtained.

The alkene anilines which are used as intermediates in carrying out the process (d) according to the invention are generally defined by the formula (VIII). In this formula (VIII), R and R ^{1 are} preferred, particularly preferably or very particularly preferably those meanings which have already been described in connection with the description of the compounds of the formula (I) according to the invention as be vorzugt, particularly preferred or very particularly preferred were specified.

alkenylanilines of formula (VIII) are known and / or can be prepared by known methods to be obtained.

in welcher
R die oben angegebenen Bedeutungen hat,
M² für M-2, M-3 oder M-4 steht,
lassen sich beispielsweise herstellen, indem man

• e) racemische Amine der Formel (III-b-rac)
  
  in welcher R und M² die oben angegebenen Bedeutungen haben, an einer chiralen stationären Kieselgelphase in Gegenwart eines Eluenten oder eines Eluenten-Gemisches als flüssiger Phase chromatographiert.

The amines of the formula (III-b)

in which
R has the meanings given above,
M ^{2 is} M-2, M-3 or M-4,
can be produced, for example, by

• e) racemic amines of the formula (III-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 an eluent mixture as the liquid phase.

The racemic amines of the formula (III-b-rac) are known and / or can after known processes (see for example WO 02/38542, EP-A 1 036 793 and EP-A 0 737 682).

Method (b)

The during execution the method according to the invention (b) needed as starting materials racemic compounds are general through the formula (I-rac) Are defined. In this formula, R, M and A are preferred, especially preferred or very particularly preferred for those meanings which already in connection with the description of the compounds according to the invention of the formula (I) for these radicals are preferred, particularly preferred or very particular were preferred.

The during execution the method according to the invention (b) racemic compounds of the formula (I-rac) are used known and can be prepared by known methods (see. e.g. WO 03/010149, WO 02/38542 and DE-A 102 29 595). racemic Compounds of formula (I-rac) may be e.g. to be obtained by giving carboxylic acid derivatives of the formula (II) with racemic compounds of the formulas (III-a-rac) or (III-b-rac) in analogy to the process according to the invention (a) implements.

In carrying out the process (b) according to the invention, the methods of preparative chromatography are used, preferably by the method of high performance liquid chromatography (HPLC). In this case, a chiral stationary silica gel phase is used. To be particularly suitable for the separation of compounds of formula (I-rac) into the two enantiomers Chiracel OD ^® has been found. This release material is commercially available. However, other stationary phases can also be used as chromatography material.

Should Compounds of the formula (I-rac) by means of fractional crystallization are separated into the individual optically active compounds are suitable generally all optically active to form diastereomeric salts Acids. Examples include: (1S) - (+) - 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, preferred of course occurring optically active amino acids.

Method (c)

Using 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, the process (c) according to the invention can be illustrated by the following equation:

The during execution the method according to the invention (c) needed as starting materials Compounds are generally defined by formulas (IV) and (V). In these formulas, R, M and A are preferred, especially preferred or very particularly preferably those meanings that already in connection with the description of the compounds according to the invention of the formula (I) for these radicals are preferred, particularly preferred or very particular were preferred.

• f) Carbonsäure-Derivate der Formel (II)
  
  in welcher A die oben angegebenen Bedeutungen hat und X¹ für Halogen oder Hydroxy steht, entweder mit einem Alkenanilin der Formel (VIII)
  
  in welcher R und R¹ die oben angegebenen Bedeutungen haben, oder mit einem Alkenanilin der Formel (IX)
  
  in welcher R und R¹ die oben angegebenen Bedeutungen haben, gegebenenfalls in Gegenwart eines Katalysators, gegebenenfalls in Gegenwart eines Kondensationsmittels, gegebenenfalls in Gegenwart eines Säurebindemittels und gegebenenfalls in Gegenwart eines Verdünnungsmittels umsetzt, oder
• g) Carboxamide der Formel (X)
  
  in welcher M und A die oben angegebenen Bedeutungen haben, und Y für Brom oder Iod steht, mit einem Alken der Formel (VII)
  
  in welcher R die oben angegebenen Bedeutungen hat, oder einem Alken der Formel (XI)
  
  in welcher R die oben angegebenen Bedeutungen hat, in Gegenwart eines Katalysators, gegebenenfalls in Gegenwart einer Base und gegebenenfalls in Gegenwart eines Verdünnungsmittels umsetzt.

Compounds of formula (IV) and (V) (or mixtures of these compounds) are obtained by reacting

• f) carboxylic acid derivatives of the formula (II)
  
  in which A has the meanings given above and X ^{1 is} halogen or hydroxyl, either with an alkenaniline of the formula (VIII)
  
  in which R and R ^{1 have} the meanings given above, or with an alkenaniline of the formula (IX)
  
  in which R and R ^{1 have} the abovementioned meanings, 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 abovementioned meanings, and Y represents bromine or iodine, with an alkene of the formula (VII)
  
  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, if appropriate in the presence of a base and, if appropriate, in the presence of a diluent.

The to carry out the method according to the invention (f) needed as starting materials Carboxylic acid derivatives of the formula (II) are already described in connection with process (a) Service.

The to carry out the method according to the invention (f) further required as starting materials alkene anilines of the formula (VIII) are already described in connection with process (d) Service.

The alkene anilines which are alternatively required as starting materials for carrying out the process (f) according to the invention are generally defiencted by the formula (IX). In this formula (IX), R and R ^{1 have} preferably, more preferably or very particularly preferably those meanings which, in connection with the description of the compounds of the formula (I) according to the invention for these radicals, are preferred, particularly preferred or very particular were preferred.

alkenylanilines of the formula (IX) are known and / or can by known methods to be obtained.

The to carry out the method according to the invention (g) needed as starting materials Carboxamides are generally defined by the formula (X). In this Formula (X) preferably has M and A, more preferably or completely particularly preferred are those meanings that are already related with the description of the compounds of the formula of the invention (I) for these radicals are preferred, particularly preferred or very particular were preferred.

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

The to carry out the method according to the invention (g) furthermore alkenes of the formula (VII) required as starting materials have already been described in connection with process (d).

The to carry out the method according to the invention (g) alternatively required as starting materials alkenes are by the Formula (XI) generally defined. In this formula (XI), R has preferred particularly preferably or very particularly preferably those meanings already in connection with the description of the compounds of the invention of the formula (I) for this radical as preferred, particularly preferred or very particular were preferred.

alkenes of the formula (XI) are known or can be prepared by known methods to be obtained.

reaction conditions

When thinner to carry out the inventive method (a) and (f) are all inert organic solvents into consideration. For this belong preferably aliphatic, alicyclic or aromatic hydrocarbons, such as. Petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, Benzene, toluene, xylene or decalin; halogenated hydrocarbons, such as. Chlorobenzene, dichlorobenzene, dichloromethane, chloroform, Carbon tetrachloride, dichloroethane or trichloroethane; Ethers, such as diethyl ether, Diisopropyl ether, methyl 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 Hexamethylphosphoramide.

The processes (a) and (f) according to the invention are optionally carried out in the presence of a suitable acid acceptor. As such, all customary inorganic or organic bases are suitable. These preferably include alkaline earth metal or Allcalimetallhydride, hydroxides, amides, alkoxides, acetates, carbonates or bicarbonates, such as sodium hydride, sodium amide, sodium methoxide, sodium ethoxide, potassium tert-butoxide, sodium hydroxide, potassium hydroxide , Ammonium hydroxide, sodium acetate, potassium acetate, calcium acetate, ammonium acetate, sodium carbonate, potassium carbonate, potassium hydrogencarbonate, sodium bicarbonate or ammonium carbonate, and tertiary amines such as trimethylamine, triethylamine, tri butylamine, N, N-dimethylaniline, N, N-dimethylbenzylamine, pyridine, N-methylpiperidine, N-methylmorpholine, N, N-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclononene (DBN) or diazabicycloundecene (DBU).

The inventive method (a) and (f) are optionally in the presence of a suitable condensing agent carried out. As such, everyone usually comes for such Amidation reactions usable condensing agent in question. Examples which may be mentioned are acid halide formers such as phosgene, phosphorus tribromide, phosphorus trichloride, phosphorus pentachloride, Phosphorus oxychloride or thionyl chloride; Anhydride formers such as ethyl chloroformate, methyl chloroformate, chloroformate, isobutylchloroformate or methanesulphonyl chloride; Carbodiimides, such as N, N'-dicyclohexylcarbodiimide (DCC) or other common Condensing agents, such as phosphorus pentoxide, polyphosphoric acid, N, N'-carbonyldiimidazole, 2-ethoxy-N-ethoxycarbonyl-1,2-dihydroquinoline (EEDQ), triphenylphosphine / carbon tetrachloride or bromotripyrrolidinophosphonium hexafluorophosphate.

The inventive method (a) and (f) are optionally carried out in the presence of a catalyst. For example may be mentioned 4-dimethylaminopyridine, 1-hydroxy-benzotriazole or Dimethylformamide.

The Reaction temperatures can during execution the inventive method (a) and (f) in a wider range be varied. In general, one works at temperatures of 0 ° C to 150 ° C, preferably at temperatures of 0 ° C up to 80 ° C.

to execution the method according to the invention (A) to prepare the compounds of formula (I) is set pro mol of the carboxylic acid derivative of the formula (II) is generally 0.2 to 5 mol, preferably 0.5 to 2 moles of aniline derivative of the formula (III).

to execution the method according to the invention (f) for the preparation of the compounds of formulas (IV) and (V) one per mole of the carboxylic acid derivative of the formula (II) is generally 0.2 to 5 mol, preferably 0.5 to 2 moles of alkenaniline of formula (VIII) or (IX).

When Eluents arrive at the execution the method according to the invention (b) all usual ones inert, organic solvents and mixtures of these, or also mixtures of these with water in question. Preferably usable are optionally halogenated aliphatic, alicyclic or aromatic hydrocarbons, such as petroleum ether, hexane, heptane, cyclohexane; Dichloromethane, chloroform; Alcohols, such as methanol, ethanol, propanol; Nitriles, such as acetonitrile; Esters such as methyl acetate or ethyl acetate. Particular preference is given to using aliphatic hydrocarbons, such as hexane or heptane, and alcohols, such as methanol or propanol, most preferably n-heptane and isopropanol or mixtures of these.

The Reaction temperatures can during execution the method according to the invention (b) each in a larger area be varied. In general, one works at temperatures between 10 ° C and 60 ° C, preferably between 10 ° C and 40 ° C, particularly preferably at room temperature.

at the implementation the method according to the invention (b) generally becomes about 1% solution of the racemic compound (I-rac) for the chromatographic separation used. It is also possible, however, others To use concentrations. The workup is carried out according to customary Methods. Generally acts one in such a way that the eluate largely narrows, solid components filtered off and dried after washing with n-heptane. The residue is optionally chromatographically of possibly still existing Impurities freed. In this case, mixtures are used as eluents n-hexane or cyclohexane and ethyl acetate used, whose Adjusted composition of each compound to be purified Need to become.

When thinner to carry out the first step of the process (d) and the inventive method (g) all inert organic solvents are suitable. For this belong preferably 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 triamide.

The first step of the process (d) according to the invention and the process (g) according to the invention are optionally carried out in the presence of a suitable acid acceptor. As such, everyone comes conventional inorganic or organic bases in question. These preferably include alkaline earth metal or alkali metal hydrides, hydroxides, amides, alkoxides, acetates, carbonates or bicarbonates, such as sodium hydride, sodium amide, sodium methoxide, sodium ethoxide, potassium tert-butoxide, sodium hydroxide, potassium hydroxide, ammonium hydroxide , Sodium acetate, potassium acetate, calcium acetate, ammonium acetate, sodium carbonate, potassium carbonate, potassium bicarbonate, sodium bicarbonate or 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), diazabicyclononene (DBN) or diazabicycloundecene (DBU).

Of the first step of the method according to the invention (d) and the inventive method (g) are carried out in the presence of one or more catalysts. To Palladium salts or complexes are particularly suitable. Come to this preferably palladium chloride, palladium acetate, tetrakis (triphenylphosphine) palladium or bis (triphenylphosphine) -palladium dichloride. It can also a palladium complex can be generated in the reaction mixture, when a palladium salt and a complex ligand are separated for reaction admits. The ligands used are preferably organophosphorus compounds question. Examples include: triphenylphosphine, tri-o-tolylphosphine, 2,2'-bis (diphenylphosphino) -1,1'-binaphthyl, Dicyclohexylphosphinebiphenyl, 1,4-bis (diphenylphosphino) butane, Bisdiphenylphosphinoferrocene, di (tert-butylphosphino) biphenyl, Di (cyclohexylphosphino) biphenyl, 2-dicyclohexylphosphino-2'-N, N-dimethylaminobiphenyl, Tricyclohexylphosphine, tri-tert-butylphosphine. But it can too to dispense with ligands.

Of the first step of the method according to the invention (d) and the inventive method (g) are further optionally in the presence of a further metal salt, such as copper salts, for example, copper (I) iodide performed.

The Reaction temperatures can during execution the first step of the process (d) and the inventive method (g) in a wider range be varied. In general, one works at temperatures of 20 ° C to 180 ° C, preferably at temperatures from 50 ° C to 150 ° C.

to execution of the first step of the process (d) according to the invention for the preparation the alkene anilines of the formula (VIII) are added per mole of the aniline derivative of the formula (VI) generally 1 to 5 mol, preferably 1 to 3 mol of alkene of the formula (VII).

to execution the method according to the invention (g) for the preparation of the compounds of formulas (IV) and (V) in general 1 to 5 mol per mole of carboxamide of the formula (X), preferably 1 to 3 moles of alkene of formula (VII) or (XI).

When thinner to carry out the method according to the invention (C) and the second step (hydrogenation) of the method according to the invention (d) all inert organic solvents are suitable. For this belong preferably aliphatic or alicyclic hydrocarbons, such as. Petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane or decalin; Ethers, such as diethyl ether, diisopropyl ether, methyl tert-butyl ether, Methyl tertiary 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.

Of the second step (hydrogenation) of the process (d) according to the invention is described in Presence of a catalyst carried out. As such, everyone comes Catalysts in question for Hydrogenations usually be used. Examples include: Raney nickel, palladium, Ruthenium or platinum, optionally on a carrier material, such as. Activated carbon.

The chiral hydrogenation in carrying out the process (c) according to the invention and in process (d) is carried out in the presence of an optically active ligand. Examples include the 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 take place in the presence of hydrogen in combination with a catalyst be carried out in the presence of triethylsilane.

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

The inventive method (C) and the second step of the process (d) is under a hydrogen pressure between 0.5 and 200 bar, preferably between 2 and 50 bar, more preferably carried out between 3 and 10 bar.

When Eluents arrive at the execution of the third step of the process (d) or of the invention inventive method (e) all usual ones inert, organic solvents and mixtures of these or also possibly mixtures with water in question. Preferably usable optionally halogenated aliphatic, alicyclic or aromatic Hydrocarbons, such as petroleum ether, hexane, heptane, cyclohexane; Dichloromethane, chloroform; Alcohols, such as methanol, ethanol, propanol; Nitriles, such as acetonitrile; Esters such as methyl acetate or ethyl acetate. Particular preference is given to using aliphatic hydrocarbons, such as hexane or heptane, and alcohols, such as methanol or propanol, most preferably n-heptane and isopropanol or mixtures of these.

The Reaction temperatures can during execution of the third step of the process (d) or of the invention inventive method (e) each in a larger area be varied. In general, one works at temperatures between 10 ° C and Preferably 60 ° C between 10 ° C and 40 ° C, especially preferably at room temperature.

at the implementation of the third step of the process (d) or of the invention inventive method (e) will generally be about 1% solution of the racemic compound (III-a-rac) or (III-b-rac) for the chromatographic separation used. It is also possible, however, others To use concentrations. The workup is carried out by conventional methods. Generally acts one in such a way that the eluate largely narrows, solid components filtered off and dried after washing with n-heptane. The residue is optionally chromatographically of any impurities still present freed. The eluents are mixtures of n-hexane and cyclohexane and ethyl acetate used, whose composition of each compound to be purified need to be adjusted.

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

The Inventive substances have a strong microbicidal action and can be used to combat undesirable Microorganisms, such as fungi and bacteria, in crop protection and be used in the protection of materials.

fungicides can plant protection be used to combat Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes. Bactericides can be used in crop protection for fighting of Pseudomonadaceae, Rhizobiaceae, Enterobacteriaceae, Corynebacteriaceae and Streptomycetaceae.

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

The active ingredients according to the invention also have a strong restorative Effect in plants. They are therefore suitable for mobilization plant's own defenses against infestation by unwanted Microorganisms.

Under plant-strengthening (resistance-inducing) substances are in the present context to understand such substances that are capable of the immune system of plants to stimulate so that the treated plants at subsequent inoculation with unwanted microorganisms extensive resistance unfold against these microorganisms.

Under undesirable Microorganisms in the present case are phytopathogenic fungi, To understand bacteria and viruses. The substances according to the invention can So be used to plants within a period of time after the treatment against the infestation by the mentioned pathogens to protect. The period within which protection is provided extends in the Generally from 1 to 10 days, preferably 1 to 7 days after Treatment of plants with the active ingredients.

The good plant tolerance the active ingredients in the fight of plant diseases necessary concentrations allows one Treatment of above-ground parts of plants, of plant and seed, and of the soil.

there can be the active compounds of the invention with particular success in combating cereal diseases, such as. against Puccinia species and diseases in wine, fruit and and vegetable growing, like e.g. against Botrytis, Venturia or Alternaria species.

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

The active ingredients according to the invention can optionally in certain concentrations and application rates also as herbicides, for influencing plant growth, as well as for fight of animal pests be used. Where appropriate, they may also be considered as intermediate and precursors for use the synthesis of other drugs.

According to the invention, all plants and parts of plants can be treated. In this context, plants are understood as meaning all plants and plant populations, such as desired and undesired wild plants or crop plants (including naturally occurring crop plants). Crop plants can be plants 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 varieties which can or can not be protected by plant breeders' rights. Plant parts are to be understood as meaning all aboveground and subterranean parts and organs of the plants, such as shoot, leaf, flower and root, examples of which include leaves, needles, stems, stems, flowers, fruiting bodies, fruits and seeds, and 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 according to the invention the plants and plant parts with the active ingredients are made directly or by affecting their environment, habitat or storage space the usual Treatment methods, e.g. by dipping, spraying, evaporating, misting, Sprinkle, spread and propagate material, in particular in seeds, further by single or multi-layer wrapping.

in the Material protection can be the substances of the invention for the protection of technical Materials against infestation and destruction by unwanted microorganisms deploy.

Under technical materials are non-living in the present context Understand materials for the use has been prepared in the art. For example can technical materials, by the active compounds according to the invention before microbial change or destruction protected adhesives, glues, paper and board, textiles, Leather, wood, paints and plastics, coolants and other materials that are infested by microorganisms or can be decomposed. As part of the protected Materials are also parts of production plants, such as cooling water circuits, called, which can be affected by the proliferation of microorganisms. As part of of the present invention are preferred as engineering materials Adhesives, glues, papers and cartons, leather, wood, paints, coolant and heat transfer fluids called, more preferably wood.

When Microorganisms that cause degradation or alteration of engineering materials can cause are for example bacteria, fungi, yeasts, algae and slime organisms called. The active compounds according to the invention preferably act against fungi, especially molds, wood-discolouring and wood-destroying fungi (Basidiomycetes) and against slime organisms and algae.

There may be mentioned, for example, microorganisms of the following genera:
Alternaria, such as Alternaria tenuis,
Aspergillus, such as Aspergillus niger,
Chaetomium, such as Chaetomium globosum,
Coniophora, like Coniophora puetana,
Lentinus, like 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, like Escherichia coli,
Pseudomonas, such as Pseudomonas aeruginosa,
Staphylococcus, such as Staphylococcus aureus.

The Active ingredients can dependent on from their respective physical and / or chemical properties in the usual Formulations are transferred, like solutions, Emulsions, suspensions, powders, foams, pastes, granules, aerosols, Very fine encapsulation in polymeric substances and in encapsulants for seeds, as well as ULV cold and warm mist formulations.

These formulations are prepared in a known manner, for example by mixing the active compounds with extenders, ie liquid solvents, liquefied gases under pressure and / or solid carriers, optionally with the use of surface-active agents, ie emulsifiers and / or dispersants and / or foam-forming agents. In the case of using water as extender, for example, organic solvents can also be used as auxiliary solvents. Suitable liquid solvents are essentially: aromatics such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, eg petroleum fractions, alcohols such as butanol or glycol and their Ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulfoxide, and water. By liquefied gaseous diluents or carriers are meant those liquids which are gaseous at normal temperature and under normal pressure, for example aerosol propellants, such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide. Suitable solid carriers are: for example ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatoms enerde and synthetic minerals, such as finely divided silica, alumina and silicates. As solid carriers for granules are: for example, broken and fractionated natural rocks such as calcite, pumice, marble, sepiolite, dolomite and synthetic granules of inorganic and organic flours and granules of organic material such as sawdust, coconut shells, corn cobs and tobacco stalks. Suitable emulsifiers and / or foam-formers 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, arylsulfonates and protein hydrolysates. Suitable dispersants are: for example lignin-sulphite liquors and methylcellulose.

It can in the formulations adhesives such as carboxymethylcellulose, natural and synthetic powdery, granular or latex-shaped Polymers such as gum arabic, polyvinyl alcohol, Polyvinyl acetate, as well as natural Phospholipids, such as cephalins and lecithins, and synthetic phospholipids. Further Additives can mineral and vegetable oils be.

It can 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 are used.

The Formulations generally contain between 0.1 and 95 weight percent Active ingredient, preferably between 0.5 and 90%.

The active ingredients according to the invention can as such or in their formulations also in mixture with known Fungicides, bactericides, acaricides, nematicides or insecticides used, e.g. to widen the spectrum of action or to prevent development of resistance. In many cases you get it synergistic effects, i. the effectiveness of the mixture is greater than the effectiveness of the individual components.

When Mischpartner come, for example, the following compounds in question:

fungicides:

• 2-phenylphenol; 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; chinomethionat; Chlobenthiazone; Chlorfenazole; chloroneb; chlorothalonil; chlozolinate; Clozylacon; cyazofamid; cyflufenamid; cymoxanil; cyproconazole; cyprodinil; cyprofuram; Dagger G; debacarb; dichlofluanid; dichlone; dichlorophen; diclocymet; Diclomezine; dicloran; diethofencarb; Difenoconazole; 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 (albesil; iodocarb; ipconazole; iprospectin; iprodiol; isoprothiolane; isovalic dione; kasugamycin; kresoxim-methyl; mancozeb; maneb; meferimzone; mepanipyrim; mepronil; metalaxyl; metalaxyl-M; metconazole; methasulfocarb; methfuroxam; metiram Metominostrobin; Metsulfovax; Mildiomycin; Myclobutanil; Myclozolin; Natamycin; Nicobifen; Nitrothal-isopropyl; Noviflumuron; Nuarimol; Ofurace; Orysastrobin; Oxadixyl; Oxolinic acid; Oxpoconazole; Oxycarboxin; Oxyfenthiine; Paclobutrazole; Pefurazoate; Penconazole; Pencycuron; Phosdiphene; Phthalide; Picoxystrobin; piperine; polyoxins; polyoxorim; Probenazole; Prochloraz; Procymidone; Propamocarb; Propanosine-sodium; Propiconazole; Propineb; Proquinazid; Prothioconazole; Pyraclostrobin; Pyrazophos; Pyrifenox; Pyrimethanil; Pyroquilon; Pyroxyfur; Pyrrolidonitrile; Quinconazole; Quinoxyfen; Quintozene; Simeconazole; Spiroxamine; sulfur; tebuconazole; tecloftalam; tecnazene; tetcyclacis; tetraconazole; thiabenda Zole; Thicyofen; Thifluzamide; Thiophanate-methyl; thiram; Tioxymid; Tolclofos-methyl; Tolyl fluoride; 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-propynyl] oxy] -3-methoxyphenyl] ethyl] -3-methyl-2 - [(methylsulfonyl) amino] butanamide ; 1- (1-naphthalenyl) -1H-pyrrole-2,5-dione; 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine; 2-Ami no-4-methyl-N-phenyl-5-thiazolecarboxamide; 2-chloro-N- (2,3-dihydro-1,1,3-trimethyl-1H-inden-4-yl) -3-pyridinecarboxamides; 3,4,5-trichloro-2,6-pyridinedicarbonitrile; Actinovate; cis-1- (4-chlorophenyl) -2- (1H-1,2,4-triazol-1-yl) cycloheptanol; Methyl 1- (2,3-dihydro-2,2-dimethyl-1H-inden-1-yl) -1H-imidazole-5-carboxylate; Monokaliumcarbonat; N- (6-methoxy-3-pyridinyl) -cyclopropanecarboxamide; N-butyl-8- (1,1-dimethylethyl) -1-oxaspiro [4.5] decan-3-amine; sodium tetrathiocarbonate; and copper salts and preparations, such as Bordeaux mixture; copper; copper naphthenate; copper oxychloride; Copper sulfate; Cufraneb; copper; mancopper; Oxine-copper.

bactericides:

• Bronopol, dichlorophen, nitrapyrin, nickel dimethyldithiocarbamate, Kasugamycin, octhilinone, furancarboxylic acid, oxytetracycline, probenazole, Streptomycin, tecloftalam, copper sulphate and other copper preparations.

Insecticides / acaricides / nematicides:

• Abamectin, ABG-9008, Acephate, Acequinocyl, Acetamiprid, Acetoprole, Acrinathrin, AKD-1022, AKD-3059, AKD-3088, Alanycarb, Aldicarb, Aldoxycarb, Allethrin, Allethrin 1R-isomers, Alpha-cypermethrin (alpha-methine), Amidoflumet, Aminocarb, Amitraz, Avermectin, AZ-60541, Azadirachtin, Azamethiphos, Azinphos-methyl, Azinphos-ethyl, Azocyclotin, Bacillus popilliae, Bacillus sphaericus, Bacillus subtilis, Bacillus thuringiensis, Bacillus thuringiensis strain EG-2348, Bacillus thuringiensis strain GC-91, Bacillus thuringiensis strain NCTC-11821, Baculoviruses, Beauveria bassiana, Beauveria tenella, Benclothiaz, Bendiocarb, Benfuracarb, Bensultap, Benzoximate, Beta-Cyfluthrin, Beta-Cypermethrin, Bifenazates, Bifenthrin, Binapacryl, Bioallethrin, Bioallethrin-S-cyclopentylisomer, Bioethanomethrin , Biopermethrin, Bioresmethrin, Bistrifluron, BPMC, Brofenprox, Bromophos-ethyl, Bromopropylate, Bromfenvinfos (-methyl), BTG-504, BTG-505, Bufencarb, Buprofezin, Butathiofos, Butocarboxim, Butoxycarboxim, Butylpyridaben, cadusafos, camphechlor, carbaryl, carbofuran, carbophenothione, carbosulfan, cartap, CGA-50439, quinomethionate, chlordane, chlordimeform, chloethocarb, chloroethoxyfos, chlorfenapyr, chlorfenvinphos, chlorofluorazuron, chlormephos, chlorobenzilates, chloropicrin, chloroproxyfen, chlorpyrifos-methyl, chlorpyrifos ( -ethyl), chlovaporthrin, chromafenozide, cis-cypermethrin, cis-resmethrin, cis-permethrin, clocythrin, cloethocarb, clofentezine, clothianidin, clothiazoben, codlemone, coumaphos, cyanofenphos, cyanophos, cycloprene, cycloprothrin, cydia pomonella, cyfluthrin, cyhalothrin, cyhexa tin, cypermethrin, cyphenothrin (1R-trans-isomer), cyromazine, DDT, deltamethrin, demeton-S-methyl, demeton-S-methylsulphone, diafenthiuron, dialifos, diazinon, dichlofenthione, dichlorvos, dicofol, dicrotophos, dicyclanil, diflubenzuron, dimefluthrin , Dimethoates, dimethylvinphos, dinobutone, dinocap, dinotefuran, diofenolane, disulfonone, docusate-sodium, dofenapine, DOWCO-439, eflusilanate, emame ctin, emamectin benzoate, empenthrin (1R isomer), endosulfan, entomopthora spp., EPN, esfenvalerate, ethiofenecarb, ethiprole, ethion, ethoprophos, etofenprox, etoxazole, etrimfos, famphur, fenamiphos, fenazaquin, fenbutatin oxide, fenfluthrin, fenitrothion, Fenobucarb, fenothiocarb, fenoxacrim, fenoxycarb, fenpropathrin, fenpyrad, fenpyrithrin, fenpyroximate, fensulfothion, fenthione, fentrifanil, fenvalerate, fipronil, flonicamid, fluacrypyrim, fluazuron, flubenzimines, flubrocythrinates, flucycloxuron, flucythrinates, flufenerim, flufenoxuron, flufenprox, flumethrin, flupyrazofos, Flutenzin (Fluffine), Fluvalinate, Fonofos, Formetanate, Formothion, Fosmethilane, Fosthiazate, Fubfenprox (Fluproxyfen), Furathiocarb, Gamma-Cyhalothrin, Gamma-HCH, Gossyplure, Grandlure, Granuloseviruses, Halfenprox, Halofenozide, HCH, HCN-801, Heptenophos, Hexaflumuron, hexythiazox, hydramethylnone, hydroprene, IKA-2002, imidacloprid, imiprothrin, indoxacarb, iodofenofen, Iprobenfos, isazofos, isofenphos, iso procarb, isoxathione, ivermectin, japonilure, kadethrin, nuclear polyhedrosis, kinoprenes, lambda-cyhalothrin, lindane, lufenuron, malathion, mecarbam, mesulfenfos, metaldehyde, metam-sodium, methacrifos, methamidophos, metharhizium anisopliae, metharhizium flavoviride, methidathion, methiocarb, methomyl, Methoprene, Methoxychlor, Methoxyfenozide, Metofluthrin, Metolcarb, Metoxadiazone, Mevinphos, Milbemectin, Milbemycin, MKI-245, MON-45700, Monocrotophos, Moxidectin, MTI-800, Naled, NC-104, NC-170, NC-184, NC 194, NC-196, niclosamide, nicotine, nitenpyram, nithiazine, NNI-0001, NNI-0101, NNI-0250, NNI-9768, novaluron, noviflumuron, OK-5101, OK-5201, OK-9601, OK-9602, OK-9701, OK-9802, omethoate, oxamyl, oxydemeton-methyl, Paecilomyces fumosoroseus, parathion-methyl, parathion (-ethyl), permethrin (cis-, trans-), petroleum, PH-6045, phenothrin (1R-trans isomer ), Phenthoate, Phorate, Phosalone, Phosmet, Phosphamidone, Phosphocarb, Phoxim, Piperonyl butoxide, Pirimicarb, Pirimiphos-methyl, Piri miphos-ethyl, Potassium oleates, Prallethrin, Profenofos, Profuthrin, Promecarb, Propaphos, Propargites, Propetamphos, Propoxur, Prothiofos, Prothoates, Protrifenbute, Pymetrozines, Pyraclofos, Pyresmethrin, Pyrethrum, Pyridaben, Pyralidyl, Pyridapenthione, Pyridathion, Pyrimidifen, Pyriproxyfen, Quinalphos , Resmethrin, RH-5849, Ribavirin, RU-12457, RU-15525, S-421, S-1833, Salithion, Sebufos, SI-0009, Silafluofen, Spinosad, Spirodiclofen, Spiromesifen, Sulfluramid, Sulfotep, Sulprofos, SZI-121 , Tau Fluvalinate, Tebufenozide, Tebufenpyrad, Tebupirimfos, Teflubenzuron, Tefluthrin, Temephos, Temivinphos, Terbam, Terbufos, Tetrachlorvinphos, Tetradifon, Tetramethrin, Tetramethrin (1R-isomer), Tetra sul, theta-cypermethrin, thiacloprid, thiamethoxam, thiapronil, thiatriphos, thiocyclamhydric oxalate, thiodicarb, thiofanox, thiometone, thiosultap-sodium, thuringiensin, tolfenpyrad, tralocythrin, tralomethrin, transfluthrin, triarathene, triazamate, triazophos, triazuron, trichlorethylene, trichlorofon , Trichoderma atroviride, triflumuron, trimethacarb, vamidothione, vaniliprole, verbutin, verticillium lecanii, WL-108477, WL-40027, YI-5201, YI-5301, YI-5302, XMC, xylylcarb, ZA-3274, zeta-cypermethrin, zolaprofos , ZXI-8901, the compound 3-methyl-phenyl-propylcarbamate (Tsumacide Z), the compound 3- (5-chloro-3-pyridinyl) -8- (2,2,2-trifluoroethyl) -8-aza-bicyclo [3.2.1] octane-3-carbonitrile (CAS Reg. No. 185982-80-3) and the corresponding 3-endo isomer (CAS Reg. No. 185984-60-5) (see WO 96/37494, WO 98/25923), as well as preparations containing insecticidal plant extracts, nematodes, fungi or viruses.

Also a mixture with other known active substances, such as herbicides or with fertilizers and growth regulators, safeners or semiochemicals is possible.

Furthermore have the compounds of the invention the formula (I) also very good antifungal effects. she have a very broad antimycotic spectrum of action, in particular against dermatophytes and yeasts, mold and diphasic fungi (e.g., against Candida species such as Candida albicans, Candida glabrata) and Epidermophyton floccosum, Aspergillus species such as Aspergillus niger and Aspergillus fumigatus, Trichophyton species such as Trichophyton mentagrophytes, Microsporon species such as Microsporon canis and audouinii. The list this mushroom does not under any circumstances limit the detectable mycotic Spectrum, but has only explanatory character.

The Active ingredients can as such, in the form of their formulations or the ones prepared from them Application forms, such as ready-to-use solutions, suspensions, wettable powders, Pastes, soluble Powder, dusts and granules are applied. The application happens in usual Way, e.g. by pouring, squirting, spraying, Scattering, dusting, foaming, Brushing, etc. It is also possible to apply the active ingredients according to the ultra-low-volume method or the active ingredient preparation or the active ingredient itself in the soil to inject. It can also be the seed of the plants to be treated.

At the Use of the active compounds according to the invention as fungicides can the application rates depending on the type of application within a larger area be varied. In the treatment of plant parts are the Application rates of active ingredient generally between 0.1 and 10,000 g / ha, preferably between 10 and 1,000 g / ha. In the seed treatment the application rates of active ingredient are generally between 0.001 and 50 grams per kilogram of seed, preferably between 0.01 and 10 g per kilogram of seed. When treating the soil are the Application rates of active ingredient generally between 0.1 and 10,000 g / ha, preferably between 1 and 5,000 g / ha.

As already mentioned above, can According to the invention, all plants and their parts are treated. In a preferred embodiment are wild or by conventional biological breeding methods, such as crossing or protoplast fusion obtained plant species and Treated plant varieties and their parts. In a further preferred embodiment are transgenic plants and plant varieties produced by genetic engineering Methods if necessary in combination with conventional methods were obtained (Genetically Modified Organisms) and their parts treated. The term "parts" or "parts of plants "or" plant parts "has been explained above.

Especially plants according to the invention are preferred the respective commercial or plant varieties in use. Among plant varieties one understands plants with new characteristics ("Traits"), which by both conventional breeding, by mutagenesis or by recombinant DNA techniques are. This can Be varieties, breeds, biotypes and genotypes.

ever according to plant species or plant varieties, their location and growth conditions (Floors, Climate, vegetation period, nutrition) can by the treatment according to the invention also superadditives ("Synergistic") effects occur. For example, reduced application rates and / or expansions of the Spectrum of action and / or an increase in the effect of the invention can be used Substances and agents, better plant growth, increased tolerance across from high or low temperatures, increased tolerance to dryness or against water or Soil salt content, increased flowering performance, facilitated harvest, acceleration of maturity, higher crop yields, higher quality and / or higher Nutritional value of Harvested products, higher Shelf life and / or workability of the harvested products possible, beyond the actually expected Go beyond effects.

The preferred transgenic (genetically engineered) to be treated according to the invention Plants or plant varieties include all plants that have been genetically engineered to obtain genetic material conferring particular beneficial traits on such plants, such as better plant growth, increased tolerance to high or low temperatures, increased tolerance to Drought or against water or soil salt content, increased flowering efficiency, easier harvesting, acceleration of ripeness, higher crop yields, higher quality and / or higher nutritional value of the harvested products, higher shelf life and / or workability of the harvested products Further and particularly highlighted examples of such properties are an increased defense of the plants against animal and microbial pests, as against insects, mites, phytopathogenic fungi, bacteria and / or viruses as well as an increased tolerance of the plants against certain herbicidal active substances Transgenic plants are the major crops, such as cereals (wheat, rice), corn, soybean, potato, cotton, tobacco, oilseed rape and fruit plants (with the fruit apples, pears, citrus fruits and grapes) mentioned, with corn, soy, potato, cotton , Tobacco and oilseed rape. Traits which are particularly emphasized are the increased defense of the plants against insects, arachnids, nematodes and snails by toxins which are formed in the plants, in particular those which are produced by the genetic material from Bacillus thuringiensis (for example by the genes CryIA (a) , CryIA (b), CryIA (c), CryIIA, CryIIIA, CryIIIB2, Cry9c Cry2Ab, Cry3Bb and CryIF and their combinations) in the plants (hereafter "Bt plants"). Traits also highlight the increased defense of plants against fungi, bacteria and viruses by systemic acquired resistance (SAR), systemin, phytoalexins, elicitors and resistance genes and correspondingly expressed proteins and toxins. ) are further particularly emphasized the increased tolerance of the plants to certain herbicidal active ingredients, for example imidazolinones, sulfonylureas, glyphosate or phosphinotricin (eg "PAT" gene). Each having the desired properties ( "traits") conferring genes can occur together in the transgenic plants in combination. Examples of "Bt plants" are maize varieties, cotton varieties, soya bean varieties and potato varieties may be mentioned that corn under the trade names YIELD GARD ^® (eg , cotton, soybeans), KnockOut ^® (for example maize), StarLink ^® (for example maize), Bollgard ^® (cotton), Nucoton ^® (cotton) and NewLeaf ^® (potato). Examples of herbicide-tolerant plants are maize varieties, cotton varieties and soybean varieties may be mentioned that against under the trade names Roundup Ready ^® (tolerance to glyphosate, for example maize, cotton, soya bean), Liberty Link ^® (tolerance to phosphinotricin, for example oilseed rape), IMI ^® (tolerance Imidazolinone) and STS ^® (tolerance to sulfonylureas such as corn) are sold. Herbicide-resistant (conventionally grown on herbicide tolerance) plants are also the varieties marketed under the name Clearfield ^® (eg corn) mentioned. Of course, these statements also apply to future or future marketed plant varieties with these or future developed genetic traits.

The listed Plants can particularly advantageous according to the invention with the compounds of the general Treated formula (I) or the drug mixtures according to the invention become. The specified in the active ingredients or mixtures above Preferential ranges also apply to the treatment of these plants. Particularly emphasized is the Plant treatment with the compounds specifically listed herein or mixtures.

The Production and use of the active compounds according to the invention is based on 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 of n-heptane / Isopropanol 9: 1 (v / v = volume / volume) dissolved. Subsequently, the solution is chromatographed fractionally on the silica gel phase Chiralcel OD ^® [Manufacturer: Daicel (Japan), column dimensions: 500 mm × 40 mm (ID), particle size: 20 μm, flow rate: 40 ml / min] with n-heptane / isopropanol 9: 1 (v / v) as eluent according to the principle of High Performance Liquid Chromatography (HPLC). In order to separate the entire amount, 5 ml (corresponding to 40 mg each of the racemate) are added to the column every 30 minutes. The detection of the compounds is carried out with a UV detector at a wavelength of 210 nm. The eluate fractions are pooled according to analytical tests to enantiomeric purity, 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, v / v in each case).

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

The enantiomeric purity of the carboxamides of formula (I) was determined by analytical HPLC under the following conditions: Phase: Chiralcel OD ^® (Daicel, Japan); 5 μm Pillar: 250 mm × 4.6 mm (ID) eluent: n-heptane / 2-propanol 10: 1 Flow rate: 0.5 ml / min UV detection: 210 nm

Analogous Example 1, as well as according to the information in the general process descriptions are the compounds of formula given in Table 1 below (I) received.

Table 1

The Determination of in the above tables and production examples specified logP values Complies with the EEC Directive 79/831 Annex V.A8 by HPLC (High Performance Liquid Chromatography) at a phase reversal column (C 18). Temperature: 43 ° C.

The Determination in the acidic range at pH 2.3 with 0.1% aqueous phosphoric acid and acetonitrile as eluent; linear gradient of 10% acetonitrile to 90% acetonitrile.

The Calibration is carried out with unbranched alkan-2-ones (having 3 to 16 carbon atoms), their logP values are known (determination of the logP values based on the retention times by linear interpolation between two consecutive alkanones).

The lambda max values were determined on the basis of the UV spectra from 200 nm to 400 nm in the maxima of the chromatographic signals. Application Examples 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 Preparation of a suitable preparation of active ingredient 1 part by weight of active compound is mixed with the stated amounts solvent and emulsifier and diluted concentrate with water to the desired concentration.

to exam Protective effectiveness of young plants with the preparation of active ingredient sprayed in the specified rate. After the spray coating has dried on are the plants with an aqueous Spore suspension of the apple mildew pathogen Podosphaera leucotricha inoculated. The plants are then in the greenhouse at about 23 ° C and a Relative humidity of about 70%.

Beispiel B Sphaerotheca-Test (Gurke)/protektiv Lösungsmittel: 24,5 Gewichtsteile Aceton 24,5 Gewichtsteile Dimethylacetamid Emulgator: 1 Gewichtsteil Alkylarylpolyglykolether 10 days after the inoculation the evaluation takes place. In this case, 0% means an efficiency which corresponds to that of the control, while an efficiency of 100% means that no infestation is observed. Table A Podosphaera test (apple) / protective

Example B Sphaerotheca test (cucumber) / protective Solvent: 24.5 parts by weight of acetone 24.5 parts by weight of dimethylacetamide emulsifier: 1 part by weight of alkylaryl polyglycol ether

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

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

Tabelle B Sphaerotheca-Test (Gurke)/protektiv

Tabelle B Sphaerotheca-Test (Gurke)/protektiv

Beispiel C Venturia-Test (Apfel)/protektiv Lösungsmittel: 24,5 Gewichtsteile Aceton 24,5 Gewichtsteile Dimethylacetamid Emulgator: 1 Gewichtsteil Alkyl-Aryl-Polyglykolether 7 days after the inoculation the evaluation takes place. In this case, 0% means an efficiency which corresponds to that of the control, while an efficiency of 100% means that no infestation is observed. Table B Sphaerotheca test (cucumber) / protective

Table B Sphaerotheca test (cucumber) / protective

Table B Sphaerotheca test (cucumber) / protective

Example C Venturia test (apple) / protective Solvent: 24.5 parts by weight of acetone 24.5 parts by weight of dimethylacetamide emulsifier: 1 part by weight of alkyl-aryl-polyglycol ether

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

to exam Protective effectiveness of young plants with the preparation of active ingredient sprayed in the specified rate. After the spray coating has dried on are the plants with an aqueous Conidia suspension of the apple scab pathogen Venturia inaequalis inoculated and then remain for 1 day at about 20 ° C and 100% relative humidity in an incubation cabin.

The Plants are then grown in the greenhouse at about 21 ° C and a relative humidity of about 90%.

Tabelle C Venturia-Test (Apfel)/protektiv

Tabelle C Venturia-Test (Apfel)/protektiv

Beispiel D Botrytis – Test (Bohne)/protektiv Lösungsmittel: 24,5 Gewichtsteile Aceton 24,5 Gewichtsteile Dimethylacetamid Emulgator: 1 Gewichtsteil Alkyl-Aryl-Polyglykolether 10 days after the inoculation the evaluation takes place. In this case, 0% means an efficiency which corresponds to that of the control, while an efficiency of 100% means that no infestation is observed. Table C Venturia test (apple) / protective

Table C Venturia test (apple) / protective

Table C Venturia test (apple) / protective

Example D Botrytis test (bean) / 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 Preparation of a suitable preparation of active ingredient 1 part by weight of active compound is mixed with the stated amounts solvent and emulsifier and diluted concentrate 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, 2 small pieces of agar covered with Botrytis cinerea are placed on each leaf. The inoculated plants will be in a darkened ten chamber at about 20 ° C and 100% relative humidity.

Tabelle D Botrytis-Test (Bohne)/protektiv

Tabelle D Botrytis-Test (Bohne)/protektiv

Beispiel E Alternaria-Test (Tomate)/protektiv Lösungsmittel: 24,5 Gewichtsteile Aceton 24,5 Gewichtsteile Dimethylacetamid Emulgator: 1 Gewichtsteil Alkyl-Aryl-Polyglykolether 2 days after the inoculation, the size of the infestation spots on the leaves is evaluated. In this case, 0% means an efficiency which corresponds to that of the control, while an efficiency of 100% means that no infestation is observed. Table D Botrytis test (bean) / protective

Table D Botrytis test (bean) / protective

Table D Botrytis test (bean) / protective

Example E Alternaria test (tomato) / 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 Preparation of a suitable preparation of active ingredient 1 part by weight of active compound is mixed with the stated amounts solvent and emulsifier and diluted concentrate with water to the desired concentration.

to exam Protective effectiveness of young plants with the preparation of active ingredient sprayed in the specified rate. After the spray coating has dried on are the plants with an aqueous Spore suspension of Alternaria solani inoculated. The plants are then incubated in an incubation cabin at about 20 ° C and 100 % relative humidity.

3 Days after the inoculation the evaluation takes place. This means 0% an efficiency equal to that of the control while a Efficiency of 100% means that no infestation is observed.

Table E Alternaria test (tomato) / protective

Claims (8)

Optically active carboxamides of the formula (I)

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

wherein the bond marked with * is linked to the amide, while the bond marked # is linked to the alkyl side chain, R ^{1 is} hydrogen, fluorine, chlorine, methyl or trifluoromethyl, A is the radical of the formula (A1)

R ^{2 is} methyl, trifluoromethyl or difluoromethyl, R ^{3 is} hydrogen, fluorine or chlorine, or A is the radical of the formula (A2)

R ^{4 is} trifluoromethyl, chlorine, bromine or iodine, or A is the radical of formula (A3)

R ^{5 is} methyl, trifluoromethyl or difluoromethyl. Optically active carboxamides of the formula (I) according to Claim 1, in which R represents hydrogen, methyl or ethyl, M represents M-1 or M-2, R ^{1 represents} hydrogen, fluorine, chlorine, methyl or trifluoromethyl, R ² is methyl or trifluoromethyl, R ^{3 is} hydrogen or fluorine, R ^{4 is} trifluoromethyl or iodine, R ^{5 is} trifluoromethyl. Process for preparing optically active carboxamides of the formula (I) according to Claim 1, characterized in that a) carboxylic acid derivatives of the formula (II)

in which A has the meanings given in claim 1 and X ^{1 is} halogen or hydroxyl, with an amine of the formula (III)

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 a liquid phase, or fractionally crystallized with optically active acids with salt formation and then the enantiomerically pure or enriched compound of the formula (I), or c) compounds of the formula (IV)

in which R, M and A have the meanings given in claim 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 hydrogenated. Means to fight undesirable Microorganisms characterized by a content of at least an optically active carboxamide of the formula (I) according to claim 1 in addition to extenders and / or surfactants. Use of optically active carboxamides of the formula (I) according to claim 1 for fighting undesirable Microorganisms. Method for fighting undesirable Microorganisms, characterized in that one optically active Carboxamides of the formula (I) according to claim 1 on the microorganisms and / or their habitat auszustingt. Method for producing means for controlling unwanted Microorganisms, characterized in that one optically active Carboxamides of the formula (I) according to claim 1 mixed with extenders and / or surfactants. Amines of the formula (III

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