WO2001014322A1 - Cycloalkylalkane carboxylic acid amides, the production and use thereof - Google Patents

Abstract

The present invention relates to novel cycloalkylalkane carboxylic acid amides of general formula (I), wherein the substituents have the following meaning: A is C3-C6-cycloalkyl which can carry one to three substituents selected from the group consisting of halogen and C1-C3-alkyl, whereby one of said substituents is positioned at the ring linking position for the cyanacetamide chain; R1 C1-C6-alkyl or C2-C6-alkenyl, whereby said radicals can be partially or entirely halogenated and/or can carry one or two of the following groups: C1-C4-alkoxy, C1-C4-halogenalkoxy, C1-C4-alkylthio, C1-C4-alkoxycarbonyl, C3-C6-cycloalkyl and phenyl, whereby the phenyl can be partially or entirely halogenated and/or can carry one to three of the following radicals: nitro, cyano, C1-C4-alkyl, C1-C4-halogenalkyl, C1-C4-alkoxy, C1-C4-halogenalkoxy, C1-C4-alkylthio, C3-C6-cycloalkyl or heterocyclyl; R2 is hydrogen or independent thereof one of the meanings of the radical R1; Y is cyano or halogen; W is phenyl, naphthyl or heteroaryl, whereby said radicals can carry one to three of the following groups: nitro, halogen, cyano, C¿1?-C4-alkyl, C1-C4-halogen-alkyl,C1-C4-alkoxy, C1-C4-halogenalkoxy, C1-C4-alkylthio, C3-C6-cycloalkyl and C1-C4-alkoxycarbonyl.

Description

 Cycloalkylalkanecarboxamides, their preparation and use

description

The present invention relates to new cycloalkylalkanecarboxamides of the general formula I

in which the substituents have the following meaning:

AC -C ₆ cycloalkyl, which one to three

Can carry substituents selected from the group consisting of halogen and Cχ-C ₃ alkyl; wherein one of these substituents is positioned at the ring linkage to the cyanoacetamide chain;

R ¹ -C ₆ -alkyl or C ₂ -C ₆ -alkenyl, these radicals being partially or completely halogenated and / or carrying one or two of the following groups: -C-alkoxy, -C-C ₄ -haloalkoxy, Cι-C ₄ alkylthio, Cι-C ₄ -alkoxycarbonyl, C ₃ -C ₆ cycloalkyl and phenyl, wherein the phenyl may be partially or fully halogenated and / or may carry one to three of the following radicals: nitro, cyano, Cι- C ~ ₄ alkyl, _{Cι-C4-haloalkyl,} Cι-C ₄ -alkoxy, C ₄ haloalkoxy, Cι-C ₄ alkylthio, C ₃ -C ₆ -cycloalkyl or heterocyclyl;

R ^{2 is} hydrogen or one of the meanings of the radical R ¹ ;

Y cyano or halogen;

W phenyl, naphthyl or heteroaryl, where these radicals can carry one to three of the following groups: nitro, halogen, cyano, C 1 -C ₄ alkyl, C 1 -C ₄ halogen alkyl, C 1 -C ₄ alkoxy, C 1 -C ₄ -haloalkoxy, -CC alkyl thio, C ₃ -C ₆ cycloalkyl and -CC ₄ alkoxycarbonyl.

Α-Halogen and α-cyano-substituted carboxamides for combating harmful fungi, in particular for combating Pyricularia oryzae, are already known from the literature (JP-A 57 185202, JP-A 57 188552, JP-A 57 188551, JP-A 58 029751, JP-A 58 029752, WO 95/31432, JP-A 07 206608, JP-A 07 330511, JP-A 08 012508 and US 4,946,867). In J. Pestic. Be. 12, 79-84 (1987), papers are published that concern the α-halogen-substituted carboxamides that have been published to date. There is also an attempt to establish quantitative structure-activity relationships for this fungicide class.

No. 4,946,867 mentions a cyanoacetamide derivative with an α-position cyclopentyl group, N- [1- (4-chlorophenyl) ethyl] -2-cyano-2-cyclopentylethanamide. WO 98/41499 mentions a cyanoacetamide derivative with an α-methyl group on the cyclopentyl ring, N [1- (4-chlorophyl) ethyl] 2-cyano-2- (2-methylcyclopentyl) acetamide.

Since the fungicidal properties of the known compounds, with regard to their activity against harmful fungi, e.g. Pyricularia oryzae, not always fully satisfying, it was the object of the present invention to protect against harmful fungi such as e.g. Pyricularia oryzae to find more effective carboxamides.

The present invention accordingly relates to the novel cycloalkylalkanecarboxamides I defined at the outset. Furthermore, the invention relates to processes for the preparation of the compounds I and the intermediates of the formula II required for their preparation. The invention furthermore relates to compositions which comprise the compounds I and processes for combating them of harmful fungi with the compounds I and finally the use of the compounds I for combating harmful fungi.

Depending on the substitution pattern, the compounds of the formula I can contain one or more centers of chirality. They are then available as mixtures of enantiomers and diastereomers. The invention relates both to the pure enantiomers or diastereomers and to their mixtures.

In the definition of the compounds I given at the beginning, collective terms were used for the radicals R ¹ and R ² , A, W and Y, which stand for individual lists of the individual group members. The radicals alkyl, alkylthio, alkoxy, alkoxycarbonyl and alkenyl can in principle each be straight-chain or branched.

The radical cycloalkyl in the definition of A denotes a C ₃ -C ₆ cycloalkyl group which is substituted on the same carbon atom which carries the group -CHY-CO-NH-CR ¹ R ² W by halogen or Cχ-C ₃ alkyl is. In the case of the radical definition cyclopentyl, for example, this corresponds to the empirical formula C ₅ H ₈ . The expression "partially or completely halogenated" is intended to express that the hydrogen atoms in the groups characterized in this way can be replaced in part or in full by identical or different halogen atoms. The meaning of halogen stands for fluorine, chlorine, bromine or iodine.

Furthermore, for example:

C ₁ -C ₄ -Alkyl, and the alkyl parts of -C-C ₄ -alkylthio: methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl and 1, 1-dimethylethyl;

-C ₆ alkyl:

C 1 -C ₄ -alkyl, as mentioned above, and pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2, 2-dimethylpropyl,

1-ethylpropyl, hexyl, 1, 1-dimethylpropyl, 1, 2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1, 1-dimethylbutyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 2, 2-dimethylbutyl, 2, 3-dimethylbutyl, 3, 3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1, 1, 2-trimethylpropyl, 1-ethyl-l-methylpropyl and l-ethyl-3-methylpropyl;

_{Cι-C4-haloalkyl:} a Cι-C ₄ -alkyl radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and / or iodine, eg chloromethyl, dichloromethyl, tri- chloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl , Chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2,2-difluoroethyl, 2, 2, 2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2 , 2-difluoroethyl, 2, 2-dichloro-2-fluoroethyl, 2, 2, 2-trichloroethyl, pentafluoroethyl, 2-fluoropropyl, 3-fluoropropyl, 2, 2-difluoropropyl, 2, 3-difluoropropyl, 2-chloropropyl , 3-chloropropyl, 2, 3-dichloropropyl, 2-bromopropyl, 3-bromopropyl, 3, 3, 3-trifluoropropyl, 3, 3, 3-trichloropropyl, 2, 2, 3, 3, 3-pentafluoropropyl, heptafluoropropyl , 1- (fluoromethyl) -2-fluoroethyl, 1- (chloromethyl) -2-chloroethyl, 1- (bromomethyl) -2-bromomethyl, 4-fluorobutyl, 4-chlorobutyl, 4-bromobutyl and nonafluorobutyl;

- C _! -C ₄ alkoxy and the alkoxy parts of -C-C ₄ alkoxycarbonyl: methoxy, ethoxy, propoxy, 1-methylethoxy, butoxy, 1-methylpropoxy, 2-methylpropoxy and 1, 1-dimethylethoxy;

C _! -C ₄ -haloalkoxy: a Cι-C ₄ alkoxy radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and / or iodine, ie, for example fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorodifluoromethoxy, Bromdi-

ÜSAΓZBLÄΓT (RULE 26) fluoromethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2-bromomethoxy, 2-iodoethoxy, 2, 2-difluoroethoxy, 2, 2, 2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2, 2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2-trichloroethoxy, pentafluoroethoxy, 2-fluoropropoxy, 3-fluoropropoxy, 2-chloropropoxy,

3-chloropropoxy, 2-bromopropoxy, 3-bromopropoxy, 2,2-difluoropropoxy, 2,3-difluoropropoxy, 2,3-dichloropropoxy, 3,3,3-trifluoropropoxy, 3, 3, 3-trichloropropoxy, 2, 2, 3, 3, 3-pentafluoropropoxy, heptafluoropropoxy, 1- (fluoromethyl) -2-fluoroethoxy, 1- (chloromethyl) -2-chloroethoxy, 1- (bromomethyl) -2-bromethoxy, 4-fluorobutoxy, 4- Chlorobutoxy, 4-bromobutoxy and nonafluorobutoxy;

C -C ₆ alkenyl: ethylene, prop-1-en-1-yl, prop-2-en-1-yl, 1-methylethenyl, buten-1-yl, buten-2-yl, buten-3-yl .

1-methyl-prop-1-en-l-yl, 2-methyl-prop-1-en-l-yl, 1-methyl-prop-2-en-l-yl and 2-methyl-prop-2- en-l-yl, penten-1-yl, penten-2-yl, penten-3-yl, penten-4-yl, 1-methyl-but-1-en-l-yl, 2-methyl-but- l-en-l-yl, 3-methyl-but-1-en-l-yl, l-methyl-but-2-en-l-yl, 2-methyl-but-2-en-l-yl, 3-methyl-but-2-en-l-yl, 1-methyl-but-3-en-l-yl, 2-methyl-but-3-en-l-yl, 3-methyl-but-3- en-l-yl, 1, l-dimethyl-prop-2-en-l-yl, 1, 2-dimethyl-prop-1-en-l-yl, 1, 2-dimethyl-prop-2-en- l-yl, 1-ethyl-prop-l-en-2-yl, l-ethyl-prop-2-en-l-yl, hex-1-en-l-yl,

Hex-2-en-l-yl, hex-3-en-l-yl, hex-4-en-l-yl, hex-5-en-l-yl, 1-methyl-pent-l-en- l-yl, 2-methyl-pent-1-en-l-yl, 3-methyl-pent-l-en-l-yl, 4-methyl-pent-1-en-l-yl, l-methyl pent-2-en-l-yl, 2-methyl-pent-2-en-l-yl, 3-methyl-pent-2-en-l-yl, 4-methyl-pent-2-en-l- yl, l-methyl-pent-3-en-l-yl, 2-methyl-pent-3-en-l-yl, 3-methyl-pent-3-en-l-yl, 4-methyl-pent 3-en-l-yl, l-methyl-pent-4-en-l-yl, 2-methyl-pent-4-en-l-yl, 3-methyl-pent-4-en-l-yl, 4-methyl-pent-4-en-l-yl, 1, l-dimethyl-but-2-en-l-yl, 1, l-dimethyl-but-3-en-l-yl, 1, 2- Dimethyl-but-1-en-1-yl, 1, 2-dimethyl-but-2-en-1-yl, 1, 2-dimethyl-but-3-en-1-yl, 1, 3-dimethyl but-1-en-1-yl, 1, 3-dimethyl-but-2-en-1-yl, 1, 3-dimethyl-but-3-en-1-yl, 2, 2-dimethyl-but- 3-en-1-yl, 2, 3-dimethyl-but-1-en-1-yl, 2, 3-dimethyl-but-2-en-1-yl, 2, 3-dimethyl-but-3- en-l-yl, 3,3-dimethyl-but-l-en-l-yl, 3,3-dimethyl-but-2-en-l-yl, 1-ethyl-but-l-en-l- yl, l-ethyl-but-2-en-l-yl, 1-ethyl-but-3-en-l-yl, 2-ethyl-but-l-en-l-yl, 2-ethyl-but- 2-en-l-yl, 2-ethyl but-3-en-l-yl, 1, 1, 2-trimethyl-prop-2-en-l-yl, l-ethyl-l-methyl-prop-2-en-l-yl, l-ethyl 2-methyl-prop-1-en-l-yl and l-ethyl-2-methyl-prop-2-en-l-yl;

ERSÄTZBIÄΓΓ (RULE 26) C ₃ -C 6 cycloalkyl: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl;

Heteroaryl: aromatic mono- or polycyclic radicals, which in addition to carbon ring members can additionally contain 1 to 4 nitrogen atoms or 1 to 3 nitrogen atoms and one oxygen or one sulfur atom or one oxygen or one sulfur atom, e.g .:

5-membered heteroaryl containing 1 to 3 nitrogen atoms: 5-ring heteroaryl groups which, in addition to carbon atoms, can contain 1 to 3 nitrogen atoms as ring members, e.g. 2-pyrrolyl, 3-pyrrolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-imidazolyl, 4-imidazolyl, 1, 2, 4-triazol-3-yl and 1, 3, 4-triazol-2- yl;

5-membered heteroaryl containing 1 to 4 nitrogen atoms or 1 to 3 nitrogen atoms and 1 sulfur atom or oxygen atom or 1 oxygen or 1 sulfur atom: 5-ring heteroaryl groups which, in addition to carbon atoms 1 to 4

Nitrogen atoms or 1 to 3 nitrogen atoms and 1 sulfur or oxygen atom or 1 oxygen or sulfur atom as ring members, e.g. 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyrrolyl, 3-pyrrolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 3-isothiazolyl, 4-isothiazolyl,

5-isothiazolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-imidazolyl, 4-imidazolyl, 1, 2, 4-oxadiazol-3-yl, l, 2,4-oxadiazol-5-yl, 1, 2, 4-thiadiazol-3-yl, 1,2, 4-thiadiazol-5-yl, 1, 2, 4-triazol-3-yl, 1, 3, 4-oxadiazol-2-yl, 1, 3,4-thiadiazol-2-yl, 1, 3, 4-triazol-2-yl;

Benzo-condensed 5-membered heteroaryl, containing 1 to 3 nitrogen atoms or 1 nitrogen atom and / or an oxygen or sulfur atom: 5-ring heteroaryl groups which, in addition to carbon atoms, contain 1 to 4 nitrogen atoms or 1 to 3 nitrogen atoms and 1 sulfur or oxygen atom or may contain 1 oxygen or sulfur atom as ring members, and in which 2 adjacent carbon ring members or 1 nitrogen and 1 adjacent carbon ring member may be bridged by a buta-1, 3-diene-1,4-diyl group;

5-membered heteroaryl bonded via nitrogen, containing 1 to 4 nitrogen atoms, or 5-membered heteroaryl, bonded via nitrogen, containing 1 to 3 nitrogen atoms: 5-ring heteroaryl groups which, in addition to

ERSAΓZBLÄΓT (RULE 26) Carbon atoms can contain 1 to 4 nitrogen atoms or 1 to 3 nitrogen atoms as ring members, and in which 2 adjacent carbon ring members or a nitrogen and an adjacent carbon ring member can be bridged by a buta- 1, 3-diene-1,4-diyl group, where these rings are bound to the framework via one of the nitrogen ring members;

6-membered heteroaryl containing 1 to 3 or 1 to 4 nitrogen atoms: 6-ring heteroaryl groups which, in addition to carbon atoms, may contain 1 to 3 or 1 to 4 nitrogen atoms as ring members, e.g. 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 2-pyrazinyl, 1,3,5-triazin-2-yl, 1,2-triazin-3-yl and 1,2,4,5-tetrazin-3-yl;

benzo-fused 6-membered heteroaryl containing 1 to 4 nitrogen atoms: 6-ring heteroaryl groups in which 2 adjacent carbon ring members can be bridged by a buta-1, 3-diene-1, 4-diyl group, e.g. Quinoline, isoquinoline, quinazoline and quinoxaline.

With regard to the fungicidal activity against harmful fungi such. B. Pyricularia oryzae, cycloalkylalkane carboxamides I with the following substituents are preferred, the preference being seen individually or in combination:

The carbon atom which carries the groups R ¹ and R ² preferably has the R configuration.

Cycloalkylalkanecarboxamides I are preferred in which R ^{1 is} C ¹ -C ₆ -alkyl and R ^{2 is} either C ₁ -C ₆ -alkyl, in particular methyl, or hydrogen. Compounds I in which R ^{1 is} methyl and R ^{2 is} hydrogen are particularly preferred.

Cycloalkylalkanecarboxamides of the formula I are furthermore preferred in which W represents optionally substituted phenyl which is substituted in particular in the 2-position or in the 2 and 4 positions. Very particularly preferred is the substitution in the 4 position on the phenyl ring, and preferably there substitution by cyano or Cι-C ₄ alkoxy, in particular methoxy, but especially by C ₁ -C ₄ alkyl, especially methyl, and preferably by halogen, where here again chlorine is preferred. In addition, cycloalkylalkane carboxamides of the formula I are preferred in which W represents 1- or 2-naphthyl, which is in each case unsubstituted or substituted by one to three of the following groups: halogen, cyano, C ₁ -C ₄ -alkyl or Cι- C ₄ alkoxy. Unsubstituted 1- or 2-naphthyl or 2-naphthyl which carries one of the following groups is particularly preferred: chlorine, cyano, methyl or methoxy. Unsubstituted 2-naphthyl is particularly preferred.

Furthermore, α-chloro- or α-bromocycloalkylalkane carboxamides I (Y = bromine or chlorine) are preferred. Α-Cyancycloalkyalkanecarboxamides I (Y = cyan) are particularly preferred. In particular, α-cyancylopentylcarboxamides I (Y = cyan, n = 5) are preferred.

Cycloalkylalkane carboxamides of the formula I in which A represents a methylated cyclopentyl radical which preferably carries the methyl substituent on the carbon atom of the point of attachment of the cycloalkane ring to the residual molecule are very particularly preferred.

In particular, the compounds I compiled in the tables below are preferred with regard to their use.

Table 1

Carboxamides Ia.001 to Ia.108 of the general formula Ia

(* = Configuration of the atom marked with "*"; R = R configuration; S = S configuration; rac. = Racemic)

Table 2

Carboxamides Ib.001 to Ib.108 of the general formula Ib, in which the meanings of the combinations of Z ¹ , Z ² and "*" are given by the rows in Table 1.

Table 3

Carboxamides Ic.OOl to Ic.108 of the general formula Ic, in which the meanings of the combinations of Z ¹ , Z ² and "*" are given by the rows in Table 1.

Table 4

Carboxamides Id.001 to Id.108 of the general formula Id, in which the meanings of the combinations of Z ¹ , Z ² and "*" are given by the rows in Table 1.

Table 5

Carboxamides le.OOl to Ie.108 of the general formula le, in which the meanings of the combinations of Z ¹ , Z ² and "*" are given by the rows in Table 1.

Table 6

Carboxamides If .001 to If.108 of the general formula If, in which the meanings of the combinations of Z ¹ , Z ² and "*" are given by the rows in Table 1.

Table 7

Carboxamides Ig.001 to Ig.108 of the general formula Ig, in which the meanings of the combinations of Z ¹ , Z ² and "*" are given by the rows in Table 1.

Table 8

Carboxamides Ih.OOl to Ih.108 of the general formula Ih, in which the meanings of the combinations of Z ¹ , Z ² and "*" are given by the rows in Table 1.

According to a preferred method according to the invention, the carboxamides I

by reaction of the carboxylic acid derivatives II, o

A- JL II

with amines of formula III

won.

The amide formation takes place according to the methods known from the literature. The free carboxylic acids of the formula II, where X is hydroxy (Ila), are generally activated beforehand

Carboxylic acid derivative II, where X e.g. stands for chlorine (Ilb).

The carboxylic acids Ila can preferably also be activated in situ by directly using the carboxylic acids Ila with the addition of, for example, dicyclohexylcarbodiimide, ethyl chloroformate, diethyl cyanophosphonate, triphenylphosphine / azodi- carboxylic acid esters, 2-pyridine disulfide / triphenylphosphine, carbonyl diimidazole, thionyl chloride, phosphorus trichloride, phosphorus pentachloride, etc. In general, for example, the carbodiimides are added in equimolar amounts with respect to the carboxylic acids Ila.

The carboxylic acids are activated via acyl cyanides, for example by reacting the carboxylic acids Ila with diethyl cyanophosphonate, preferably in an inert solvent such as tetrahydrofuran, toluene or dichloromethane (cf. Tetrahedron Lett. 18 (1973) 1595-8).

Activation via anhydrides is carried out, for example, by reacting the carboxylic acids Ila with carbonic acid chlorides such as ethyl chloroformate in general in the presence of bases and, if appropriate, in an inert solvent such as toluene or tetrahydrofuran (cf. "Houben-Weyl", 4th edition (1974), 15/1 page 28-32).

Amide formation is preferably carried out in the presence of bases such as tertiary amines, e.g. Triethylamine or dirnethylcyclohexylamine,

Alkali metal carbonates, alkali metal hydroxides, pyridine, etc. carried out. The reactants and the auxiliary base are expediently used in equimolar amounts. A slight excess of the auxiliary base of 0.1 - 0.5 equivalents can be helpful under certain circumstances.

Aliphatic hydrocarbons such as hexane and ligroin, aromatic hydrocarbons such as toluene and xylene, chlorinated hydrocarbons such as methylene chloride and 1,2-dichloroethane, ethers such as methyl tert-butyl ether and tetrahydrofuran, polar aprotic solvents such as acetonitrile and dirnethyl formamide or esters such as ethyl acetate come as solvents or mixtures thereof in question.

The molar ratio of carboxylic acid derivatives II to amine III is generally 0.8 to 1.5 and preferably 0.9 to 1.1.

After completion of the reaction, the work-up is carried out as usual, e.g. by introducing the reaction mixture into water and then extracting the amide.

The amines of formula III are known or can easily be obtained (cf. Organikum (1993) Barth Verlagsgesellschaft mbH Leipzig, pp. 509 ff; "Houben-Weyl", volume 15/1, pages 648-665; J. Am. Chem Soc. 58, pp. 1808-1811 (1936), Indian J. Chem. 10 (1972) 366)).

ERSÄΓZBLÄΓΓ (RULE 26) The R isomer can be separated from racemates of the amines III in a manner known per se, for example by fractional crystallization with optically active tartaric acid or preferably by means of enzyme-catalyzed esterification and subsequent saponification (cf. WO-A 95/08636).

The carboxylic acid derivatives II are known from the literature and can e.g. can be produced as follows:

Commercially available cyclopentanone is converted to the Michael systems in a Knoevenagel reaction with α-halogen or α-cyanoacetic acid Ci-C _ö alkyl esters (cf. Chem. Heterocycl. Compd. 24 (1988) 860-4). The condensation is usually carried out in a water-immiscible solvent, such as hexane, toluene or xylene, with the water formed in the reaction being removed from the circle. For this purpose, the reaction mixture is heated to boiling under reflux for several hours. Bases such as piperidine, pyridine, n-octylamine, ammonia or β-alanine are used as catalysts in the presence of an acid such as glacial acetic acid. N-Octylamine is particularly preferred as the base (see also WO 00/07989).

An alkyl Grignard compound is then added to a Michael system to obtain saturated type II systems.

The reaction is carried out in solvents which are inert under the reaction conditions. Ethers such as tetrahydrofuran, diethyl ether, dirthoxyethane or methyl tert-butyl ether are particularly preferred. As a rule, a reaction temperature of from -10 to 80 ° C. and preferably from 10 to 60 ° C. is set.

The Grignard compound is generally used in equimolar amounts based on the Michael system VI. In some cases it proves advantageous to use the Grignard compound in an excess of 0.2 to 0.5 molar equivalents.

As a rule, the addition is copper-catalyzed by adding 1-10 mol% of e.g. Copper (I) iodide carried out. This results in a higher selectivity with regard to 1,2-addition versus 1,4-addition.

The free carboxylic acids Ila (X = OH) are finally produced by alkaline hydrolysis of the corresponding esters (Organikum 1993 Barth Verlagsgesellschaft mbH, Leipzig, p. 431ff.). The abovementioned processes provide carboxylic acid derivatives II which are suitable, for example, for the preparation of the carboxamides I according to the invention.

The particularly preferred embodiments of the carboxylic acid derivatives II with regard to the substituents A and Y correspond to those of the carboxamides I.

In formula II, X stands for a nucleophilically exchangeable radical, such as hydroxy, C 1 -C ₄ -alkoxy, halogen z. B. bromine or chlorine, hetaryl, for example imidazolyl or pyridyl, carboxylate, for example acetate or tri-fluoroacetate etc.

Carboxylic acid derivatives of the formula II in which the linking ring carbon atom carries a methyl group are particularly preferred.

The compounds I are distinguished by excellent activity against a broad spectrum of phytopathogenic fungi, in particular from the class of the Ascomycetes, Deuteromycetes, Phycomycetes and Basidiomycetes. Some of them are systemically effective and can be used in plant protection as leaf and soil fungicides.

They are particularly important for combating a large number of fungi on various crops such as wheat, rye, barley, oats, rice, corn, grass, bananas, cotton, soybeans, coffee, sugar cane, wine, fruit and ornamental plants and vegetables such as cucumbers, Beans, tomatoes, potatoes and squash, as well as on the seeds of these plants.

They are particularly suitable for combating the following plant diseases: Erysiphe graminis (powdery mildew) in cereals, Erysiphe cichoracearum and Sphaero theca fuliginea on pumpkin plants, Podosphaera leucotricha on apples, Uncinula neca tor on vines, Puccii-ia species on cereals, Rhizo Cotton, rice and lawn, Ustilago species on cereals and sugar cane, Venfcuria inaequalis (scab) on apples, Helmin thosporium species on cereals, Septoria nodorum on wheat, Bo trytis cinerea (gray mold) on strawberries, vegetables, ornamental plants and vines, Cercospora arachi - di cola on peanuts, Pseudocercosporella herpotrichoides on wheat, barley, Pyricularia oryzae on rice, P-ytop-iti-ora infestans on potatoes and tomatoes, Fusarium and Verfcicillium species on various plants, Plas opara vi ticola on vines, Pseudopero - nospera species on hops and cucumbers, AI ternaria species on vegetables and fruit, and Mycosphaerella species in bananas. The compounds I are also suitable for combating harmful fungi in the protection of materials (for example wood, paper, dispersions for addressing, fibers or fabrics) and in the protection of stored products.

The compounds I are used by treating the fungi or the plants, seeds, materials or the soil to be protected against fungal attack with a fungicidally active amount of the active compounds. It is used before or after the infection of the materials, plants or seeds by the fungi.

They can be converted into the usual formulations, such as solutions, emulsions, suspensions, dusts, powders, pastes and granules. The form of application depends on the respective purpose; in any case, it should ensure a fine and uniform distribution of the compound according to the invention. The formulations are prepared in a known manner, e.g. by stretching the active ingredient with solvents and / or carriers, if desired using emulsifiers and dispersants, and in the case of water as diluent other organic solvents can also be used as auxiliary solvents. The following are essentially considered as auxiliaries: solvents such as aromatics (e.g. xylene), chlorinated aromatics (e.g. chlorobenzenes), paraffins (e.g. petroleum fractions), alcohols (e.g. methanol, butanol), ketones (e.g. cyclohexanone), amines (e.g. Ethanolamine, dimethylformamide) and water; Carriers such as natural stone powder (e.g. kaolins, clays, talc, chalk) and synthetic stone powder (e.g. highly disperse silica, silicates); Emulsifiers such as non-ionic and anionic emulsifiers (e.g. polyoxyethylene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates) and dispersants such as lignin sulfite liquors and methyl cellulose.

The fungicidal compositions generally contain between 0.1 and 95, preferably between 0.5 and 90% by weight of active ingredient.

Depending on the type of effect desired, the application rates in crop protection are between 0.01 and 2.0 kg of active ingredient per ha.

In the case of seed treatment, amounts of active ingredient of 0.001 to 0.1 g, preferably 0.01 to 0.05 g, per kg of seed are generally required.

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

The agents according to the invention can also be present in the use form as fungicides together with other active ingredients, which e.g. with herbicides, insecticides, growth regulators, fungicides or even with fertilizers.

When mixed with fungicides, the fungicidal activity spectrum is enlarged in many cases.

The following list of fungicides with which the compounds according to the invention can be used together is intended to explain, but not to limit, the possible combinations:

Sulfur, dithiocarbamates and their derivatives, such as ferridimethyldithiocarbamate, zinc dimethyldithiocarbamate, zinc ethylene bisdithiocarbamate, manganese ethylene bisdithiocarbamate, manganese-zinc ethylenediamin-bis-dithiocarbamate, tetramethylthiurium -diamid-dibi-ethamidulfide ), Ammonia complex of zinc (N, N'-propylene-bis-dithiocarbamate), zinc (N, N'-propylene-bis-dithiocarbamate), N, N'-polypropylene-bis- (thio-carbamoyl) disulfide;

Nitroderivatives such as dinitro- (l-methylheptyl) phenyl crotonate, 2-sec-butyl-4, 6-dinitrophenyl-3, 3-dimethylacrylate, 2-sec-butyl-4, 6-dinitrophenyl-isopropyl carbonate, 5-nitro-isophthalic acid -di-isopropyl ester;

heterocyclic substances such as 2-heptadecyl-2-imidazoline acetate, 2,4-dichloro-6- (o-chloroanilino) -s-triazine, 0, O-diethyl-phthalimidophosphonothioate, 5-amino-l- [bis - (dimethylamino) phosphinyl] -3-phenyl-l, 2, 4-triazole, 2, 3-dicyano-l, 4-dithioanthraquinone, 2-thio-l, 3-dithiolo [4, 5-b] quinoxaline, 1- (butylcarbamoyl) -2-benzimidazole-carbamic acid methyl ester, 2-methoxycarbonylamino-benzimidazole, 2- (furyl- (2)) -benzimidazole, 2- (thiazolyl- (4)) -benzimidazole, N- (1, 1, 2, 2-tetrachloroethylthio) tetrahydrophthalimide, N-trichloromethylthio-tetrahydrophthalimide, N-trichloromethylthio-phthalimide,

N-dichlorofluoromethylthio-N ', N'-dimethyl-N-phenylsulfuric acid diamide, 5-ethoxy-3-trichloromethyl-1,2,3-thiadiazole, 2-rhodanomethylthiobenzothiazole, 1,4-dichloro-2, 5-dimethoxybenzene, 4- (2-chlorophenylhydrazono) -3-methyl-5-isoxazolone, pyridine-2-thio-1-oxide, 8-hydroxyquinoline or its copper salt, 2, 3-dihydro-5-carboxanilido-6- methyl-1,4-oxathiin, 2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiin-4,4-dioxide, 2-methyl-5,6-dihydro-4H-py-

ERSÄΓZBLAΠ (RULE 26) ran-3-carboxylic acid anilide, 2-methyl-furan-3-carboxylic acid anilide, 2, 5-dimethyl-furan-3-carboxylic acid anilide, 2,4, 5-trimethyl-furan-3-carboxylic acid anilide, 2, 5-dimethyl furan-3-carboxylic acid cyclohexyl amide, N-cyclohexyl-N-methoxy-2, 5-dimethyl-furan-3-carboxylic acid aid, 2-methyl-benzoic acid anilide, 2-iodo-benzoic acid anilide, N-formyl -N-morpholine-2, 2, 2-trichloroethyl acetal, piperazin-1, 4-diyl-bis- (1- (2, 2, 2-trichloro-ethyl) -formamide, 1- (3, 4-dichloroanilino ) -l-formylamino-2, 2, 2-trichloroethane, 2, 6-dimethyl-N-tridecylmorpholine or its salts, 2, 6-dimethyl-N-cyclododecylmorpholine or its salts, N- [3- (p-tert-butylphenyl) -2-methylpropyl] cis-2, 6-dimethyl-morpholine, N- [3- (p-tert-butylphenyl) -2-methylpropyl] piperidine, 1- [2- (2,4-dichlorophenyl) -4-ethyl-1,3-dioxolan-2-yl-ethyl] -1H-1,2,4-triazole, 1- [2- (2,4- Dichlorophenyl) -4-n-propyl-l, 3-dioxolan-2-yl-ethyl] -1H-1,2,4-triazole, N- (n-propyl) -N- (2,4,6 -trichlorphenoxyethyl ) -N'-imidazol-yl urea,

1- (4-chlorophenoxy) -3, 3-dimethyl-l- (1H-1,2,4-triazol-l-yl) -2-butanone, 1- (4-chlorophenoxy) -3, 3- dimethyl-1- (1H-1,2,4-triazol-yl) -2-butanol, (2RS, 3RS) -1- [3- (2-chlorophenyl) -2- (4-fluorophenyl) oxirane -2-ylmethyl] -1H-1,2,4-triazole, α- (2-chlorophenyl) -α- (4-chlorophenyl) -5-pyrimidine-methanol, 5-butyl-2-dimethylamino-4-hy- hydroxy-6-methyl-pyrimidine, bis- (p-chlorophenyl) -3-pyridine-methanol, 1,2-bis- (3-ethoxycarbonyl-2-thioureido) -benzene, 1,2-bis- (3-methoxycarbonyl) -2-thioureido) benzene,

Strobilurins such as methyl-E-methoxyimino- [α- (o-tolyloxy) -o-tolyl] acetate, methyl-E-2- {2- [6- (2-cyanophenoxy) pyrimidin-4-yl-oxy ] -phenyl} -3-methoxyacrylate, methyl-E-methoxyimino- [α- (2-phenoxyphenyl)] -acetamide, methyl-E-methoxyimino- [α- (2, 5-dimethylphenoxy-oxy) -o- tolyl] acetamide,

Anilinopyrimidines such as N- (4, 6-dimethylpyrimidin-2-yl) aniline, N- [4-methyl-6- (1-propynyl) pyrimidin-2-yl] aniline, N- [4-methyl -6-cyclopropyl-pyrimidin-2-yl] aniline,

Phenylpyrroles such as 4- (2,2-difluoro-1,3-benzodioxol-4-yl) pyrrole-3-carbonitrile,

Cinnamic acid amides such as 3- (4-chlorophenyl) -3- (3, 4-dimethoxyphenyl) acrylic morpholide,

as well as various fungicides, such as dodecylguanidine acetate, 3- [3- (3,5-dimethyl-2-oxycyclohexyl) -2-hydroxyethyl] glutarimide, hexachlorobenzene, DL-methyl-N- (2,6-dimethylphenyl) -N-furoyl (2) -alaninate, DL-N- (2, 6-dimethylphenyl) -N- (2'-methoxyacetyl) -alanine methyl ester, N- (2, 6- Dimethylphenyl) -N-chloroacetyl-D, L-2-aminobutyrolactone, DL-N- (2,6-dimethylphenyl) -N- (phenylacetyl) alanine methyl ester, 5-methyl-5-vinyl-3- ( 3, 5-dichlorophenyl) -2, 4-dioxo-

REPLACEMENT BLÄRT (RULE 26) 1,3-oxazolidine, 3- [3,5-dichlorophenyl (-5-methyl-5-methoxymethyl] -1,3-oxazolidine-2,4-dione, 3- (3,5-dichlorophenyl) -1-isopropylcarba - moylhydantoin, N- (3, 5-dichlorophenyl) -1, 2-dimethylcyclopropane-1, 2-dicarboximide, 2-cyano- [N- (ethylaminocarbonyl) -2-methoximino] acetamide, 1- [2- (2,4-dichlorophenyl) pentyl] -1H-1,2,4-triazole, 2,4-difluoro-α- (1H-1,2,4-triazolyl-l-methyl) -benzhydryl alcohol, N - (3-Chloro-2, 6-dinitro-4-trifluoromethyl-phenyl) -5-trifluoromethyl-3-chloro-2-aminopyridine, 1- ((bis- (4-fluorophenyl) methylsilyD-methyl ) -1H-1,2,4-triazole.

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

The active substance concentrations in the ready-to-use preparations can be varied over a wide range.

In general, they are between 0.0001 and 10%, preferably between 0.01 and 1%.

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

The amount of active ingredient used to control pests is 0.1 to 2.0, preferably 0.2 to 1.0, kg / ha under field conditions.

Mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, furthermore coal tar oils as well as oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. benzene, toluene, xylene, paraffin, are used for the production of directly sprayable solutions, emulsions, pastes or oil dispersions. Tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclohexanol, cyclohexanone, chlorobenzene, isophorone, strongly polar solvents, for example dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, water. Aqueous use forms can be prepared from emulsion concentrates, pastes or wettable powders (wettable powders, oil dispersions) by adding water. To prepare emulsions, pastes or oil dispersions, the substances as such or dissolved in an oil or solvent can be homogenized in water by means of wetting agents, adhesives, dispersants or emulsifiers. However, it is also possible to prepare concentrates which consist of an active substance, wetting agents, adhesives, dispersants or emulsifiers and possibly solvents or oil and which are suitable for dilution with water.

Alkali, alkaline earth, and ammonium salts of ligninsulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutylnaphthalenesulfonic acid, alkylarylsulfonates, come as surface-active substances.

15 alkyl sulfates, alkyl sulfonates, fatty alcohol sulfates and fatty acids and their alkali and alkaline earth salts, salts of sulfated fatty alcohol glycol ether, condensation products of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensation products of naphthalene or naphthalene sulfonic acid with

20 phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenol polyglycol ether, tributylphenyl polyglycol ether, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, ethoxylated castor oil

25 liert polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol ester, lignin sulfite liquors and methyl cellulose.

Powders, materials for broadcasting and dusts can be prepared by mixing or grinding the active substances together with a solid carrier.

The formulations generally contain between 0.01 and 95% by weight, preferably between 0.1 and 90% by weight, of the active ingredient. The active ingredients are used in a purity of 90% to 35 100%, preferably 95% to 100% (according to the NMR spectrum).

Examples of formulations are:

I. 5 parts by weight of a compound according to the invention are intimately mixed with 40 95 parts by weight of finely divided kaolin. In this way, a dust is obtained which contains 5% by weight of the active ingredient.

II. 30 parts by weight of a compound according to the invention are intimately mixed with 5 of a mixture of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which has been sprayed onto the surface of this silica gel. A preparation of the active ingredient with good adhesiveness (active ingredient content 23% by weight) is obtained in this way.

III. 10 parts by weight of a compound according to the invention are dissolved in a mixture consisting of 90 parts by weight of xylene, 6 parts by weight of the adduct of 8 to 10 moles of ethylene oxide and 1 mole of oleic acid-N-monoethanolamide, 2 parts by weight Calcium salt of dodecylbenzenesulfonic acid and 2 parts by weight of the adduct of 40 moles of ethylene oxide with 1 mole of castor oil (active ingredient content 9% by weight).

IV. 20 parts by weight of a compound according to the invention are dissolved in a mixture consisting of 60 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 5 parts by weight of the adduct of 7 moles of ethylene oxide and 1 mole of isooctylphenol and

5 parts by weight of the adduct of 40 moles of ethylene oxide with 1 mole of castor oil (active ingredient content 16% by weight).

V. 80 parts by weight of a compound according to the invention are mixed well with 3 parts by weight of the sodium salt of diisobutylnaphthalene-alpha-sulfonic acid, 10 parts by weight of the sodium salt of lignin sulfonic acid from a sulfite waste liquor and 7 parts by weight of powdered silica gel and grind in a hammer mill (active ingredient content 80% by weight).

VI. 90 parts by weight of a compound according to the invention are mixed with 10 parts by weight of N-methyl-α-pyrrolidone and a solution is obtained which is suitable for use in the form of tiny drops (active substance content 90% by weight).

VII. 20 parts by weight of a compound according to the invention are dissolved in a mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 7 moles of ethylene oxide and 1 mole of isooctylphenol and 10 parts by weight . -Share the adduct of 40 moles of ethylene oxide with 1 mole of castor oil. Pouring the solution into 100,000 parts by weight of water and finely distributing it therein gives an aqueous dispersion which contains 0.02% by weight of the active ingredient.

VIII.20 parts by weight of a compound according to the invention are pulverized with 3 parts by weight of the sodium salt of diisobutylnaphthalene-α-sulfonic acid, 17 parts by weight of the sodium salt of a lignin sulfonic acid from a sulfite waste liquor and 60 parts by weight. deformed silica gel well mixed and ground in a hammer mill. By finely distributing the mixture in 20,000 parts by weight of water give a spray liquor which contains 0.1% by weight of the active ingredient.

Granules, e.g. Coating, impregnation and homogeneous granules can be produced by binding the active ingredients to solid carriers. Solid carriers are e.g. Mineral soils, such as silica gel, silicas, silica gels, silicates, talc, kaolin, Attaclay, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as e.g. Ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and vegetable products such as corn flour, tree bark, wood and nutshell flour, cellulose powder and other solid carriers.

Various types of oils, herbicides,

Fungicides, other pesticides, bactericides, if necessary also only immediately before use (tank mix), are added. These agents can be added to the agents according to the invention in a weight ratio of 1:10 to 10: 1.

synthesis Examples

Preparation of the carboxylic acid derivatives II

example 1

2-cyano- (1-methyl-cyclopentyl) acetic acid

a) 2-Cyano-cyclopentylidene-acetic acid methyl he

235.2 g (2.8 mol) of cyclopentanone, 198 g (2 mol) of methyl cyanoacetate, 13.7 g of acetic acid (0.22 mol) and 8.8 g (0.11 mol) of onium acetate in 300 ml of benzene and refluxed for eight hours on the water separator. The reaction mixture was cooled with methyl tert. -Butyl ether, washed twice with water and dried over magnesium sulfate. After filtering off the drying agent and removing the solvent on a rotary evaporator, the product 2-cyano-cyclopentylidene-acetic acid methyl ester was isolated by distillation over a 30 cm packed column (297.7 g, 90% yield).

b) 2-Cyano- (1-methyl-cyclopentyl) -acetic acid methyl ester

100 g of methyl 2-cyanocyclopentylidene (606 mmol) and 0.7 g of copper (I) iodide in 500 ml of absolute diethyl ether were introduced under a protective gas. It was cooled to 0 ° C, then 498 ml of a 1.4 molar solution of Methylmagnesium bromide added dropwise in toluene. It was stirred overnight. For working up, the reaction solution was mixed with dilute hydrochloric acid. After stirring for one hour, the organic phase was separated and the aqueous phase with methyl tert. -butyl ether extracted. The combined organic phases were dried over magnesium sulfate and freed from the solvent on a rotary evaporator. The crude product (105 g, 96% crude yield) was distilled through a 30 cm packed column. 78 g of product were obtained (77% yield).

c) 2-cyano- (1-methyl-cyclopentyl) carboxylic acid

For the saponification, the product of the previous reaction (105 g, 629 mmol) was stirred for 12 hours in a mixture of 628 ml of 2N NaOH and 300 ml of methanol. For working up, the reaction solution was diluted with water, with methyl tert. - Butyl ether washed and then first acidified with 2 N hydrochloric acid. The mixture was then triturated three times with methyl. -butyl ether extracted, and the combined organic phases were dried over sodium sulfate and freed from the solvent on a rotary evaporator. 100 g of NMR-pure product were obtained (100% yield).

Example 2

2-cyano- (1-ethyl-cyclopentyl) acetic acid

a) 2-Cyano- (1-ethylcyclopentyl) acetic acid methyl ester

The compound was obtained analogously to Example 1b) in the course of a Grignard reaction of methyl 2-cyanocyclopentylidene acetate with EtMgBr.

b) 2-cyano- (1-ethyl-cyclopentyl) acetic acid

The ester was saponified analogously to Example lc).

Example 3

2-cyano- (1-isopropyl-cyclopentyl) acetic acid (compound II.3 in Table A)

a) 2-Cyano- (1-isopropylcyclopentyl) acetic acid methyl ester The compound was obtained analogously to Example 1b) in the course of a Griguard reaction of methyl 2-cyanocyclopentylidene acetate. The Grignard reagent was freshly prepared from 2-bromopropane and magnesium shavings.

b) 2 -Cyano- (1-isopropylcyclopentyl) acetic acid

The ester was saponified analogously to Example lc).

Example 4

2-cyano- (1-isopropenyl-cyclopentyl) acetic acid (compound II.4 in Table A)

a) 2-Cyano- (1-isopropenylcyclopentyl) acetic acid methyl ester

The compound was obtained analogously to Example 1b) in the course of a Grignard reaction of methyl 2-cyanocyclopentylidene-acetic acid.

b) 2-cyano- (1-isopropenylcyclopentyl) acetic acid

The ester was saponified analogously to Example lc).

Example 5

2-cyano- ((E / Z) -1-propenyl-cyclopentyl) -carboxylic acid (compound II.5 in Table A)

a) 2-Cyano- ((E / Z) -1-propenyl-cyclopentyl) -carboxylic acid methyl ester

The compound was obtained analogously to Example 1b) in the course of a Grignard reaction of methyl 2-cyanocyclopentylidene.

b) 2 -Cyano- ((E / Z) -1-propenyl-cyclopentyl) -carboxylic acid

The ester was saponified analogously to Example lc).

Example 6

2-cyano- (1-vinyl-cyclopentyl) carboxylic acid (Compound II.6 in Table A)

a) 2-Cyano- (1-vinyl-cyclopentyl) carboxylic acid methyl ester The compound was obtained analogously to Example 1b) in the course of a Grignard reaction of methyl 2-cyanocyclopentylidene-acetic acid.

b) 2-cyano- (1-vinyl-cyclopentyl) carboxylic acid

The ester was saponified analogously to Example lc).

Example 7

(1 -Allyl -cyclopentyl) -2 -cyanoacetic acid

a) (1-Allyl-cyclopentyl) -2-cyanoacetic acid methyl ester

The connection was analogous to Example 1b) in the course of a

Grignard implementation of methyl 2-cyanocyclopentylidene obtained.

b) (1-Allyl-cyclopentyl) -2-cyanoacetic acid

The ester was saponified analogously to Example lc).

Example 8

2-cyano- (1-propyl-cyclopentyl) carboxylic acid (Compound II.8 in Table A)

a) 2-Cyano- (1-propyl-cyclopentyl) carboxylic acid methyl ester

The connection was analogous to Example 1b) in the course of a

Grignard reaction of 2-cyanocyclopentylidene-acetic acid methyl ester obtained.

b) 2-cyano- (1-propyl-cyclopentyl) carboxylic acid

The ester was saponified analogously to Example 1c).

Preparation of the carboxamides I

Example 9

N- [1- (4-Chlorophenyl) ethyl] -2-cyano-2- (1-methyl-cyclopentyl) acetamide

To a solution of 1.0 g (6 mmol) of 2-cyano- (1-methyl-cyclopentyl) acetic acid and 0.93 g (6 mmol) of rac. 1- (4-Chlorophenyl) ethylamine in 50 ml dichloromethane became 0.6 g (6 mmol) triethylamine added. Then 0.87 g of 93% (5.4 mmol) diethyl cyanophosphonate were added dropwise at 10 ° C. and the mixture was stirred at room temperature for 12 hours. After adding 50 ml of dichloromethane, the mixture was washed with 100 ml of 2N sodium hydroxide solution, 54% hydrochloric acid and water. The organic phase was then dried and concentrated. The remaining residue was purified by chromatography on silica gel (mobile phase: cyclohexane: ethyl acetate 7: 3). 0.7 g (39% yield) of the diastereomer mixture of the title compound remained as a solid with a melting point of 130 ° C.

^X H NMR (CDC1 ₃ in ppm): 1.1; 1.5; 1.6; 1.75; 5.0; 6.2; 7.3.

Example 10

N- [1- (4-Chlorophenyl) ethyl] -2-cyano-2- (1-ethylcyclopentyl) acetamide

By reacting 2-cyano- (1-ethyl-cyclopentyl) acetic acid with R-1- (4-chlorophenyl) ethylamine, the title compound was obtained as a mixture of diastereomers as in Example 9.

Example 11

N- [1- (4-Chlorophenyl) ethyl] -2-cyano-2- (1-isopropylcyclopentyl) acetamide

By reacting 2-cyano- (1-isopropyl-cyclopentyl) acetic acid with R-1- (4-chlorophenyl) ethylamine, the title compound was obtained as a mixture of diastereomers as in Example 9.

Example 12

N- [1- (4-Chlorophenyl) ethyl] -2-cyano-2- (1-isopropenyl-cyclopentyl) acetamide

By reaction of 0.75 g (3.9 mmol) of 2-cyano- (1-isopropenyl-cyclopentyl) acetic acid and 0.61 g (3.9 mmol) of R-1 - (4-chlorophenyl) ethylamine was obtained analogously to Example 9, 0.66 g (51% yield) of the title compound as a brownish, resinous mixture of diastereomers.

* H-NMR (CDC1 ₃ , in ppm): 1.5; 1.7; 1.85; 1.95; 3.5; 5.0; 6.2; 7.25. Example 13

N- [1- (4-chlorophenyl) ethyl] -2-cyano- (E / Z) -1-propenyl-cyclopentyl-acetamide

From the reaction of 0.46 g (3.4 mmol) of 2-cyano- (E / Z) -1-propenylcyclopentyl) acetic acid with 0.47 g (2.4 mmol) of R-1- (4- Chlorophenyl) ethylamine was obtained analogously to Example 9 after chromatographic purification, 0.35 g (40% yield) of the title compound as a mixture of diastereomers.

^! H-NMR (CDC1 ₃ , in ppm): 1.48; 1.65; 1.75; 1.9; 3.4; 4.9; 5.4; 5.65; 6.15; 7.3.

Example 14

N- [1- (4-chlorophenyl) ethyl] -2-cyano-2- (1-vinyl-cyclopentyl) acetamide

By reacting 0.6 g (3.36 mmol) of 2-cyano- (1-vinyl-cyclopentyl) acetic acid and 0.52 g (3.36 mmol) of R-1- (4-chlorophenyl) ethylamine 0.38 g (36% yield) of the title compound was obtained as a mixture of diastereomers.

^X H NMR (CDCI ₃ , in ppm): 1.45; 1.65; 1.8; 2.2; 3.5; 5.0; 5.1; 5.75; 7.3.

Example 15

2- (1-allylcyclopentyl) -N- [1- (4-chlorophenylethyl)] -2-cyanoacetamide

By reacting 1.29 g (6.7 mmol) (1-allyl-cyclopentyl) -2-cyanoacetic acid with 1.04 g (6.7 mmol) of R-1- (4-chlorophenyl) ethylamine analogously to Example 9, 0.31 g (14% yield) of the title compound was obtained as a mixture of diastereomers.

ⁱ HN R (CDCI ₃ , in ppm): 1.5; 1.65; 1.8; 2.2; 3.4; 5.0; 5.8; 6.25; 7.3.

Example 16

N [1- (4-chlorophenyl) ethyl] -2-cyano-2- (1-propylcyclopentyl) acetamide

SPARE BLADE (RULE 26) By reacting 1.05 g (5.38 mmol) of 2-cyano- (1-propyl-cyclopentyl) acetic acid and 0.83 g (5.38 mmol) of R-1- (4-chlorophenyl) ethylamine analogously to Example 9, 0.68 g (38% yield) of the title compound was obtained as a mixture of diastereomers (colorless resin).

ⁱ H-NMR (CDC1 ₃ , in ppm): 0.8; 1.3; 1.6; 1.75; 3.4; 5.0; 6.3; 7.25.

Example 17

2-Cyano-N- [1- (2,4-dichlorophenyl) ethyl] -2- (1-methylcyclopentyl) acetamide

By reacting 1.0 g (6.0 mmol) of 2-cyano- (1-methyl-cyclopentyl) acetic acid and 1.1 g (6.0 mmol) of R-1- (2,4-dichlorophenyl) - ethylamine was obtained analogously to Example 9 1.2 g (60% yield) of the title compound as a mixture of diastereomers.

ⁱ H-M (CDC1 ₃ , in ppm): 1.1; 1.25; 1.55; 1.7; 3.3; 5.3; 6.4; 7.2; 7.4.

Example 18

2-cyano-N- [1- (2,4-dichlorophenyl) ethyl] -2- (1-ethylcyclopentyl) acetamide

By reacting 2-cyano- (1-ethyl-cyclopentyl) acetic acid with R-1- (2, 4-dichlorophenyl) ethylamine, the title compound was obtained as a mixture of diastereomers as in Example 9.

Example 19

2-Cyano-N- [1- (2,4-dichlorophenyl) ethyl] -2- (1-isopropylcyclopentyl) acetamide

By reacting 2-cyano- (1-isopropyl-cyclopentyl) acetic acid with R-1- (2, 4-dichlorophenyl) ethylamine, the title compound was obtained as a mixture of diastereomers as in Example 9.

Example 20

2-Cyano-N- [l- (2,4-dichlorophenyl) ethyl] -2- (1-isopropenyl-cyclopentyl) acetamide

By reacting 0.75 g (23.88 mmol) of 2-cyano- (1-isopropenylcyclopentyl) acetic acid with 0.76 g (3.88 mmol) of R-1- (2,4-dichlorophenyl) ethylamine was obtained analogously to Example 9 after chromato-

REPLACEMENT BLAΓΓ (RULE 26) graphic cleaning 0.95 g (67% yield) of the title compound as a mixture of diastereomers.

iH-NMR (CDC1 ₃ , in ppm): 1.5; 1.7; 1.9; 3.5; 4.9; 5.3; 6.5; 7.2; 7, 4.

Example 21

2-cyano-N- [l- (2,4-dichloro-phenyl) ethyl] -2- ((E / Z) -1-propenylcyclopentyl) acetamide

By reacting 0.46 g (2.4 mmol) of 2-cyano- ((E / Z) -1-propenylcyclopentyl) acetic acid and 0.47 g (2.4 mmol) of R-1- (2, 4-dichlorophenyl) ethylamine was obtained analogously to Example 9 0.35 g of the title compound (40% yield) as a mixture of diastereomers (colorless resin).

ⁱ H-NMR (CDCI ₃ , in ppm): 1.45; 1.6; 1.75; 1.9; 3.4; 5.3; 5.5; 5.85; 6.4; 7.2; 7.4.

Example 22

2-Cyano-N- [1- (2,4-dichloro-phenyl) ethyl] -2- (1-vinyl-cyclopentyl) acetamide

By reacting 0.6 g (3.36 mmol) of 2-cyano- (1-vinyl-cyclopentyl) acetic acid and 0.65 g (3.36 mmol) of R-1- (2,4-dichlorophenyl) - ethylamine was obtained analogously to Example 9 0.42 g (36% yield) of the title compound as a mixture of diastereomers (colorless resin).

ⁱ H-NMR (CDCI ₃ , in ppm): 1.35; 1.55; 1.8; 3.3; 5.2; 5.75; 6.5; 7.2; 7.4.

Example 23

2- (1-allyl-cyclopentyl) -2-cyano-N- [1 (2,4-dichlorophenyl-ethyl] acetamide

By reacting (1-allyl-cyclopentyl) -2-cyanoacetic acid with R-1- (2, 4-dichlorophenyl) ethylamine, the title compound was obtained as a mixture of diastereomers analogously to Example 9.

Example 24

2-Cyano-N- [1- (2,4-dichlorophenylethyl)] -2- (1-propylcyclopentyl) acetamide

REPLACEMENT BLAΓΓ (RULE 26) By reacting 2-cyano- (1-propyl-cyclopentyl) acetic acid with R-1- (2, 4-dichlorophenyl) ethylamine, the title compound was obtained as a mixture of diastereomers as in Example 9.

applications

The fungicidal activity of the compounds of the general formula I against harmful fungi was demonstrated by the following greenhouse tests:

The active ingredients were administered as a 20% emulsion in a mixture of 70% by weight cyclohexanone, 20% by weight Nekanil ^® LN (Lutensol ^® AP6, wetting agent with emulsifying and dispersing action based on ethoxylated alkylphenols) and 10% by weight. % Emulphor ^® EL (Emulan ^® EL, emulsifier based on ethoxylated fatty alcohols) prepared and diluted with water according to the desired concentration.

Efficacy against Pyricularia oryzae (protective)

Leaves of rice seedlings (variety "Tai-Nong 67") grown in pots were treated with the aqueous preparation of the active ingredients (containing 250 ppm). After about 24 hours, the plants were inoculated with an aqueous spore suspension of Pyricularia oryzae. The plants treated in this way were placed in climatic chambers at 22-24 ° C. and 95 to 99% relative atmospheric humidity for 6 days. The extent of the development of the infestation on the leaves was then determined visually.

In this test, those with the invention showed

Compounds Ex. 9, 12, 20, 21 treated plants an infection of 10% and less and the untreated plants 80% infection.

2. Systemic activity against Pyricularia oryzae

Pre-germinated rice (variety "Tai-Nong 67") was cultivated in a hydroponic with Hoagland solution up to the two-leaf stage. Then the roots were watered with the aqueous preparation of the active ingredients (containing 50 ppm). After five days of further cultivation in the greenhouse, the plants were inoculated with an aqueous spore suspension of Pyricularia oryzae. The plants treated in this way were placed in climatic chambers at 22-24 ° C. and 95 to 99% relative atmospheric humidity for 6 days. The extent of the development of the infestation on the leaves was then determined visually. In this test, the plants treated with the compounds according to the invention, Example 9, Example 16, showed an infection of 15% and less and the untreated plants 80%.

Comparative tests with regard to the fungicidal activity

Connections examined:

Compound A: Example 9

Compound B: State of the art according to WO 98/41499

Efficacy against Pyricularia oryzae (protective)

Result :

Evaluation:

A 50% fungal infection can be observed in the plants treated with the active ingredient B, while almost no fungal infection is observed in the plants treated with the compound A according to the invention.

4. Comparison against US 4,946,867 - systemic activity against Pyricularia oryzae

The improved fungicidal activity of the compounds of the general formula I according to the invention compared to the structurally closest compound of the prior art (US 4,946,867) was shown by the following experiment. Active ingredient A known from US Pat. No. 4,946,867 served as a comparison compound.

The test was carried out analogously to Application Example 2 with 50 or 10 ppm aqueous active ingredient preparation.

Untreated (control) plants showed an infestation of 80

Claims

claims

1. Cycloalkylalkanecarboxamides of the general formula I

in which the substituents have the following meaning:

AC ₃ -C ₆ cycloalkyl, which one to three

Can carry substituents selected from the group consisting of halogen and -CC ₃ alkyl; wherein one of these substituents is positioned at the ring linkage to the cyanoacetamide chain;

R ¹ Ci-C _ß alkyl or C ₂ -C ₆ alkenyl, these radicals being partially or completely halogenated and / or carrying one or two of the following groups:

Cχ-C ₄ alkoxy, Cι-C ₄ haloalkoxy, Cχ-C ₄ alkylthio, Cι-C-alkoxycarbonyl, C ₃ -C ₆ "cycloalkyl and phenyl, the phenyl being partially or completely halogenated and / or one to can carry three of the following residues: nitro, cyano, Ci ^ alkyl,

_{Cι-C4-haloalkyl, Cι-C4} ~ alkoxy, _{Cι-C4-haloalkoxy,} Cι-C ₄ alkylthio, C ₃ -C ₆ -cycloalkyl or heterocyclyl;

R ^{2 is} hydrogen or one of the meanings of the radical R ¹ ;

Y cyano or halogen;

W phenyl, naphthyl or heteroaryl, where these radicals can carry one to three of the following groups: nitro, halogen, cyano, C 1 -C ₄ alkyl, C 1 -C ₄ halogen alkyl, C 1 -C alkoxy, C 1 -C -Halogenalkoxy, -C -C alkyl thio, C ₃ -C ₆ cycloalkyl and -C -C ₄ alkoxycarbonyl;

and their agriculturally applicable salts.

2. Cycloalkylalkanecarboxamides of the general formula I according to claim 1, in which

A means cyclopentyl, the cyclopentyl group being substituted in the 1-position by Cχ-C ₃ alkyl.

3. Cycloalkylalkanecarboxamides of the general formula I according to claim 1 or 2, in which R ^{1 is} Ci-C _ß- alkyl.

4. Cycloalkylalkanecarboxamides of the general formula I according to one of claims 1-3, in which R ^{2 is} hydrogen.

5. Cycloalkylalkanecarboxamides according to any one of claims 1-4, wherein W represents a phenyl group which can be mono-, di- or trisubstituted by halogen, C ₁ -C ₄ alkyl, Cχ-C ₄ alkoxy or cyano.

6. Cycloalkylalkanecarboxamides according to claim 5, wherein W represents a phenyl group which is monosubstituted and the substituent is in the 2- or 4-position of the phenyl ring.

7. cycloalkylalkane carboxamides according to claim 5, wherein W represents a phenyl group which is disubstituted and the substituents are in the 2- and 4-position of the phenyl ring.

8. Cycloalkylalkanecarboxamides according to any one of claims 5-7, wherein the substituent in the 2-position is selected from halogen, C ₁ -C alkyl, Cχ-C ₄ alkoxy or cyano.

9. Cycloalkylalkanecarboxamides according to any one of claims 5-7, wherein the substituent in the 4 position is selected from chlorine,

Fluorine, cyano, C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy.

10. A process for the preparation of cycloalkylalkanecarboxylic acid amides of the general formula I according to claims 1-9, characterized in that a carboxylic acid derivative of the formula II,

in which the radicals A and Y which have the meaning given in claim 1 and X represents a nucleophilically exchangeable radical,

with an amine of formula III,

in which the radicals W, R ¹ and R ^{2 have} the meaning given in claim 1, is reacted.

11. Agent containing an effective amount for controlling harmful fungi 5 at least one cycloalkylalkanecarboxamide of the formula I according to claim 1 and at least one inert liquid and / or solid carrier and optionally at least one surface-active substance.

10 12. A method of combating harmful fungi, characterized in that the harmful fungi, their habitat or the plants, surfaces, materials or spaces which they irritate are treated with an effective amount of a cycloalkylalkane carboxamide of the formula I according to claim 1.

15

13. Use of a cycloalkylalkanecarboxamide of the general formula I according to claim 1 for combating harmful fungi.

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