MXPA99008320A - Cycloalkylalkanecarboxamides and the production and use thereof - Google Patents

Abstract

The invention relates to novel cycloalkylalkanecarboxamides of general formula (I) wherein the substituents have the following significance;A - C3-C6-cycloalkyl;R1-C1-C6-alkyl or C2-C6-alkenyl;R2, R3, R4 - hydrogen or independent of any of the meanings of the radical R1;n - 0 or 1;y - cyano or halogen;W - phenyl, naphthyl or heteroaryl. The compounds (I) are characterized by excellent efficacy against a wide range of phytopathogenic fungi, especially those belonging to the Ascomecetes, Deuteromycetes, Phycomycetes and Basidiomycetes class. The inventive compounds have a partially systemic effect and can be used in phytosanitary control as foliar and telluric fungicides.

Description

CYCLEALKILALCANCARBOXAMIDES AND THEIR PREPARATION AND USE The present invention relates novel cycloalkylalcancarBoxamides of the formula I wherein the substituents have the following meanings: A is C3-C6 cycloalkyl which may have attached thereon one to three substituents selected from the group consisting of halogen and C1-C3 alkyl; R1 is Ci-Ce alkyl or C2-C6 alkenyl, it being possible for these radicals to be partially or totally halogenated and / or to have one or two of the following groups fixed thereto: C1-C4 alkoxy, haloalkoxy C? -C4, alkylthio C? -C4 C1-C4 alkoxycarbonyl, C3-C6 cycloalkyl and phenyl, it being possible for the phenyl to be partially or fully halogenated and / or to have one to three of the following radicals fixed thereon: nitro, cyano, C? Alkyl? C4, haloa "C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkoxy, C 1 -C 4 alkylthio, C 3 -C 6 cycloalkyl or heterocyclyl; R 2, R 3, R 4 are hydrogen or, independently of this meaning, have one of the meanings of the radical R1; n is 0 or 1; And it is cyano or halogen; W is phenyl, naphthyl or heteroaryl, it being possible for these three radicals to be fixed on them from one to three of the following groups: nitro, halogen, cyano, Ci-C alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 alkylthio, C 3 -C 6 cycloalkyl and C 1 -C 4 alkoxycarbonyl, except for the compounds of the formula I wherein n is 0 and A is cyclopentyl. Alpha-halo and alpha-substituted cyanocarboxamides have already been reported in the literature to control harmful fungi, particularly to control Pyricularia oryzae (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). J. Pestic. Sci. 12 (1987), 79-84, 'compiles works related to the alpha-halo substituted carboxamides published to date. This publication also tries to establish quantitative relationships between structure and effect for the case of fungicides. US 4,946,867 mentions a cyanoacetamide derivative with a cyclopentyl group in the alpha, N- [1- (4-chlorophenyl) ethyl] -2-cyano-2-cyclopentyleneteamide position. Since the fungicidal properties of the known compounds are not always completely satisfactory in terms of their activity against harmful fungi, for example Pyricularia oryzae, it is an object of the present invention to find novel carboxamides which are more active against harmful fungi, for example, Pyricularia. oryzae We have found that this object is achieved by the novel cycloalkylalkanecarboxamides I defined at the beginning. In addition, we have found processes for the preparation of the compounds I and the intermediates of the formula II required for their preparation. We have found compositions comprising the compounds I, methods for controlling harmful fungi using the compounds I and finally the use of the compounds I to control harmful fungi. Depending on the substitution pattern, the compounds of the formula I may contain one or more chiral centers. In this case, they exist as mixtures of enantiomers and diastereomers. The invention relates to pure enantiomers and diastereomers and also to mixtures thereof. In the definition of the compounds I provided at the beginning, collective terms representing individual enumerations of each of the group members were employed for the radicals R1 to R4, A and Z. The alkyl, alkylthio, alkoxy, alkoxycarbonyl and alkenyl radicals can be straight chain or branched. The cycloalkyl radical represents the unsubstituted backbone if no specific substitution of a hydrogen by halogen or C1-C3 alkyl is mentioned. The definition of cyclopentyl radical, for example, corresponds to the empirical formula C5H10. The term "partially or totally halogenated" has the purpose of expressing that in the groups characterized, in this way, some or all of the hydrogen atoms may be replaced by identical or different halogen atoms. The meaning of halogen represents in each case fluorine, bromine or iodine. Examples of other meanings are: C 1 -C 4 alkyl and the alkyl C 1 -C 4 alkyl proportions: methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl and 1, 1-dimethylethyl; alkyl d-Cd: C 1 -C 4 alkyl, in accordance with the above, and also 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 dimethyl butyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1-trimethylpropyl, 1-ethyl-1-methylpropyl and 1-ethyl-3-methylpropyl; C1-C4 haloalkyl: a C 1 -C 4 alkyl radical according to the above mentioned partially or totally substituted by fluorine, chlorine, bromine and / or iodine, for example, chloromethyl, dichloromethyl, trichloromethyl, 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- (bromoethyl) -2-bromoethyl, 4-fluorobutyl, 4-chlorobutyl, 4-bromobutyl and nonafluorobutyl; C 1 -C 4 alkoxy and the alkoxy portions of C 1 -C 4 alkoxycarbonyl: methoxy, ethoxy, propoxy, 1-methylethoxy, butoxy, 1-methylpropoxy, 2-methylpropoxy and 1,1-dimethylethoxy; - C 1 -C 4 haloalkoxy: a C 1 -C 4 alkoxy radical according to the above mentioned partially or totally substituted by fluoro, chloro, bromo and / or iodo, for example, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorodifluoromethoxy, bromodifluoromethoxy, 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-bromomethoxy, 4-fluorobutoxy, 4-chlorobutoxy, 4-bro obutoxy and nonafluorobutoxy; C2-C2 alkenyl: ethylene, prop-1-en-l-yl, prop-2-en-l-yl, 1-methylenyl, buten-1-yl, buten-2-yl, buten-3-yl, -methylprop-1-en-l-yl, 2-methylprop-l-en-l-yl, 1-methylprop-2-en-l-yl and 2-methylprop-2-en-l-yl, penten-1 -yl, penten-2-yl, penten-3-yl, penten-4-yl, 1-methylbut-l-en-l-yl, 2-methylbut-l-en-l-yl, 3-methylbutyl -in-l-yl, 1-methylbut-2-en-l-yl, 2-methylbut-2-en-l-yl, 3-methylbut-2-en-l-yl, l-methylbut-3-en -l-yl, 2-methylbut-3-en-l-yl, 3-methylbut-3-en-l-yl, 1, l-dimethylprop-2-en-l-yl, 1,2-dimethylprop-l -in-l-yl, 1,2-dimethylprop-2-en-l-yl, l-ethylprop-l-en-2-yl, l-ethylprop-2-en-l-yl, hex-1-en -l-ilo, hex-2-en-l-yl, hex-3-en-l-yl, hex-4-en-l-yl, hex-5-l-yl, 1-methylpent-1-en -l-ilo, 2-methylpent-l-en-l-yl, 3-methylpent-1-en-l-yl, 4-methylpent-l-en-l-yl, l-methylpent-2-en-l - ilo, 2-methylpent-2-en-l-yl, 3-methylpent-2-en-l-yl, 4-methylpent-2-en-l-yl, l-methylpent-3-en-l-yl , 2-methylpent-3-en-l-yl, 3-methylpent-3-en-l-yl, 4-methylpent-3-en-l-yl, l-methylpent-4-en-l-yl or, 2-methylpent-4-en-l-yl, 3-methylpent-4-en-l-yl, 4-methylpent-4-en-l-yl, 1, 1- dimethylbut-2-en-l- ilo, 1, l-dimethylbut-3-en-l-yl, 1, 2-dimethylbut-1-en-l-yl, 1, 2-dimethylbut-2-en-l-yl, 1, 2-dimethylbutyl- 3-en-l-yl, 1,3-dimethylbut-l-en-l-yl, 1,3-dimethylbut-2-en-l-yl, 1,3-dimethylbut-3-en-l-yl, 2, 2- dimethylbut-3-en-l-yl, 2,3-dimethylbut-l-en-l-yl, 2, 3-dimethylbut-2-en-l-yl, 2,3-dimethylbut-3- en-1-yl, 3, 3-dimethylbut-1-en-1-yl, 3, 3-dimethylbut-2-en-1-yl, 1-ethylbut-1-en-1-yl, l-ethylbutyl- 2-en-l-yl, l-etlbut-en-3-yl, 1, 1, 2-trimethylprop-2-en-l-yl, l-ethyl-l-methyl-prop-2-en-l- ilo, l-ethyl-2-methyl-prop-l-en-l-yl and l-ethyl-2-methyl-prop-2-en-l-yl; C3-C6 cycloalkyl: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl; heteroaryl: monocyclic or polycyclic aromatic radicals which, in addition to the carbon ring, may additionally contain from 1 to 4 nitrogen atoms, or from 1 to 3 nitrogen atoms and an oxygen atom or a sulfur atom or an oxygen or a sulfur atom, for example: 5-membered heteroaryl containing from 1 to 3 nitrogen atoms: 5-membered heteroaryl ring groups which, in addition to the carbon atoms, may contain from 1 to 3 nitrogen atoms as ring members, for example, 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 from 1 to 4 nitrogen atoms or from 1 to 3 nitrogen atoms and a sulfur atom either an oxygen atom or an oxygen atom or a sulfur atom: heteroaryl ring groups of 5 members which, in addition to the carbon atoms, may contain from 1 to 4 nitrogen atoms or from 1 to 3 nitrogen atoms, and one sulfur atom or oxygen atom or one oxygen atom or sulfur atom as ring members, for example, 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, 1,2,4-oxadazol-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; benzofused 5-membered heteroaryl containing from 1 to 3 nitrogen atoms or a nitrogen atom and / or an oxygen or sulfur atom: 5-membered heteroaryl ring groups which, in addition to the carbon atoms, may contain 1 to 4 nitrogen atoms or 1 to 3 nitrogen atoms and one sulfur atom or one oxygen atom or one oxygen atom or one sulfur atom as ring members and in which 2 carbon ring members adjacent or a nitrogen and an adjacent carbon ring member may be bridged by a buta-1,3-dien-1,4-diyl group; a 5-membered heteroaryl bonded via nitrogen and containing 1 to 4 nitrogen atoms, or 5-membered benzofused heteroaryl bonded through nitrogen and containing 1 to 3 nitrogen atoms: heteroaryl ring groups of 5 members which, in addition to the carbon atoms, may contain from 1 to 4 nitrogen atoms or from 1 to 3 nitrogen atoms, respectively, as ring members and in which two adjacent carbon ring members or a nitrogen and an adjacent carbon ring member may be bridged by a buta-1,3-diene-1,4-diyl group, these rings are attached to the backbone through one of the nitrogen ring members; 6-membered heteroaryl containing from 1 to 3, or from 1 to 4 nitrogen atoms: 6-membered heteroaryl ring groups which, in addition to the carbon atoms, may contain from 1 to 3, or from 1 to 4, respectively, nitrogen atoms as ring members, for example, 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 2-pyrazinyl , 1, 3, 5-triazin-2-yl, 1,2,4-triazin-3-yl and 1, 2, 4, 5-tetrazin-3-yl; - benzofused 6-membered heteroaryl containing from 1 to 4 nitrogen atoms: 6-membered heteroaryl ring groups wherein two adjacent carbon ring members can be bridged by a buta-1, 3-diene-1, 4 group -diyl, for example, quinoline, isoquinoline, quinazoline and quinoxaline. Preferably, in relation to the fungicidal action against harmful fungi, for example, Pyricularia oryzae, the cycloalkylalkanecarboxamides I are present with the following substituents, preferably in each case alone or in combination: The carbon atom having fixed on it the groups R1 and R2 are preferably in the R configuration. Preferred cycloalkylalkanecarboxamides I are the cycloalkylalkancarboxamides I wherein R1 is methyl and R2 is either methyl or hydrogen; compounds I are especially preferred where R1 is methyl and R2 is hydrogen. Further preferred cycloalkancarboxamides (sic) of the formula I are those in which W is unsubstituted or substituted phenyl, substituted in particular in the 2-position or in the 2 and 4 positions. Very particularly preferably, the substitution is in the position 4 in the phenyl ring and preferably here the substitution is by cyano or methoxy, preferably substitution by methyl, and particularly by halogen, chlorine being again preferred here. In addition, cycloalkancarboxamides of the formula I are preferred in which W is 1-naphthyl or 2-naphthyl which, in each case, is unsubstituted or substituted by two to three of the following groups: halogen, cyano, C1-C4 alkyl or either C1-C4 alkoxy. Especially preferred is 1-naphthyl or unsubstituted 2-naphthyl or 2-naphthyl carrying one of the following groups: chloro, cyano, methyl or methoxy. Unsubstituted 2-naphthyl is particularly preferred. In addition, the preferred cycloalkylalkanecarboxamides I are cycloalkylalkanecarboxamides I where n = 1. Substituents R3 and R4 are preferably C1-C4 alkyl and particularly methyl or ethyl. Also preferred is the combination in which one of the two substituents is hydrogen and the other is C1-C4 alkyl, particularly methyl or ethyl. Also preferred are alpha-chloro or alpha-bromocycloalkylalkancarboxamides I (Y = bromine or chlorine). Especially preferred are alpha-cyanocycloalkylalkancarboxamides T (Y = cyano). further, cycloalkylalkancarboxamides of the formula I are preferred where A is a substituted C3-C6 cycloalkyl. Especially preferred is a methylated C3-C6 cycloalkyl radical which preferably carries the methyl substituent on the carbon linking the cycloalkane ring with the rest of the molecule. Finally, the preferred cycloalkylalkanecarboxamides of the general formula I are the cycloalkylalkancarboxamides wherein A is unsubstituted or substituted cyclopropyl. Particularly, cyclopropyl which has bound thereon one to three substituents selected from the group consisting of chloro and C1-C3 alkyl, particularly methyl. Preferably, chlorinated cyclopropyl has two chlorine atoms in the geminal position on the cyclopropane ring. Preferably, the alkylated, or preferably methylated, cyclopropyl has one of the alkyl (methyl) substituents fixed on the carbon atom at the site at which the cyclopropane ring is attached on the remaining portion. Taking into account their use, the compounds I compiled in the following tables are especially preferred. Table 1 Carboxamides la.001 to la.108 of the formula la (* = configuration of the designated atom «*»; R = R configuration; S = S configuration; rae = racemic) Table 1 No. Z1 Z2 * la.001 HHR la.002 HHS la.003 HH rae la.004 H Cl R la.005 H Cl s la.006 H Cl rae la.007 H CH3 R la.008 H CH3 s la.009 H CH3 rae la.010 H OCH3 R la.011 H OCF-S la.013 HFR la.014 HFS la.015 HF rae la.016 H CN R la.017 H CN S la.018 H CN rae la.019 Cl HR la.020 Cl HS la.021 Cl H oe the. 022 Cl Cl R.0.023 Cl Cl S la.024 Cl Cl ee la. 025 Cl CH3 R la.026 Cl CH3 S la.027 Cl CH3 rae la.028 Cl OCH3 R la.029 Cl OCH3 S la.030 Cl OCH3 rae la.031 Cl FR la.032 Cl FS la.033 Cl F rae la.034 Cl CN R la.035 Cl CN S .036 Cl CN rae la.037 CH3 HR la.038 CH3 HS la.039 CH3 H rae la.040 CH3 Cl R la.041 CH3 Cl -? la.042 CH3 Cl rae la.043 CH3 CH3 R la.044 CH3 CH3 S la.045 CH3 CH33 rae la.046 CH3 OCH3 R la.047 CH3 OCH3 S la.048 CH3 OCH3 rae la.049 CH3 FR la.050 CH33 FS la.051 CH33 F rae la.052 CH33 CN R la.053 CH33 CN S la.054 CH33 CN rae la.055 OCH3 HR la.056 OCH3 HS la.057 OCH3 H rae la.058 OCH3 Cl R la. 059 OCH3 Cl3 la.060 OCH3 Cl rae the.061 OCH3 CH3 R la.062 OCH3 CH3 S la.063 OCH3 CH3 rae la.064 OCH3 OCH3 R la.065 OCH3 OCH3 S la.066 OCH3 OCH3 rae la.067 OCH3 FR la.068 OCH3 FS la.069 OCH3 F rae la.070 OCH3 CN R la.071 OCH3 CN S la.072 OCH3 CN rae la.073 FHR la.074 FHS la.075 FH rae la.076 F Cl R la .077 F Cl S la.078 F Cl rae la.079 F CH3 R la.080 F CH3 S la.081 F CH3 rae. la.082 F OCH3 R la.083 F OCH3 S la.084 F 0CH3 rae la.085 FFR la.086 FFS la.087 FF rae la.088 F CN R la.089 F CN S la.090 F CN rae la .091 CN HR la.092 CN HS la.093 CN H rae. the .9494 CN Cl R. the .095 CN Cl S la. 096 CN Cl rae. la.097 CN CH3 R la.098 CN CH3 S la.099 CN CH3 rae. la.100 CN 0CH3 R la.101 CN 0CH3 S la.102 CN OCH3 rae. la.103 CN F R la.104 CN F S la.105 CN F rae. a.106 CN CN R.107 CN CN S.108 CN CN. Table 2 The carboxamides Ib.001 to Ib.108 of the formula Ib in which the meanings of the combinations of Z1, Z2 and «*» are indicated by the lines of Table 1.

Ib Table 3 The carboxamides Ic.001 to le.108 of the formula le where the meanings of the combinations of Z1, Z2 and «*» are indicated by the lines in Table 1.

Table 4 The carboxamides Id.001 to Id.108 of the formula Id where the meanings of the combinations of Z1, Z2 and «*» are indicated by the lines in Table 1.

Table 5"as carboxamides le.001 to le.108 of the formula le where the meanings of the combinations of Z1, Z2 and" * "are indicated by the lines in Table 1.

Table 6 The carboxamides If.001 to If.108 of the formula If where the meanings of the combinations of Z1, Z2 and «*» are indicated by the lines in Table 1.

Table 7 The carboxamides Ig.001 to Ig.108 of the formula Ig in which the meanings of the combinations of Z1, Z2 and «*» are indicated by the lines of Table 1.

Table 8 The carboxamides Ih.001 to Ih.108 of the formula Ih where the meanings of the combinations of Z1, Z2 and "*" are indicated by the lines of Table 1.

Table 9 The carboxamides Ii.001 to Ii.108 of the formula Ii where the meanings of the combinations of Z1, Z2 and «*» are indicated by the lines of Table 1.

Table 10 The carboxamides Ik.001 to Ik.108 of the formula Ik wherein the meanings of the combinations of Z1, Z2 and "*" are indicated by the lines of Table 1.

Table 11 The carboxamides Im.001 to Im.108 of the formula I in which the meanings of the combinations of Z1, Z2 and «*» are indicated by the lines of Table 1.

Im Table 12 The carboxamides In.001 to In.108. of the formula In where the meanings of the combinations of Z1, Z2 and «*» are indicated by the lines in Table 1.

Table 13 The carboxamides lo.001 to lo.108 of the formula In (sic) where the meanings of the combinations of Z1, Z2 and «*» are indicated by the lines in Table 1.

Table 14 The carboxamides Ip.001 to Ip.108 of the formula Ip in terms of the meanings of the combinations of Z1, Z2 and «*» are indicated by the lines in Table 1.

Ip Table 15 The carboxamides Iq.001 to Iq.108 of the formula Iq where the meanings of the combinations of Z1, Z2 and «*» are indicated by the lines of Table 1.

In addition, processes were found in which carboxamides I can be prepared in good yields. Table 16 The carboxamides Ir.001 to Ir.108 of the formula Ir where the meanings of the combinations of Z1, Z2 and «*» are indicated by the lines in Table 1.

Table 17 The carboxamides Is.001 to Is.108 of the formula Is in which the meanings of the combinations of Z1, Z2 and "*" are indicated by the lines of Table 1.

Table 18 The carboxamides It.001 to It.108 of the formula It where the meanings of the combinations of Z1, Z2 and «*» are indicated by the lines in Table 1.

Table 19 The carboxamides Iu.001 to Iu.108 of the formula Iu where the meanings of the combinations of Z1, Z2 and «*» are indicated by the lines in Table 1.

Table 20 Carboxamides Iv. 1 to Iv.24 of the formula Iv (the configuration of the atom marked with "*" is racemic) Table 21 Carboxamides Iw.l to I.24 of the formula I wherein the meanings of the combinations of. A, n, R3, R4 and Y are provided by the lines in Table 20. (the configuration of the atom marked "*" is R) Table 22 Carboxamides Iz.la Iz.24 of the formula Iz where the meanings of the combinations of A, n, R3, R4 and Y are given by the lines of Table 20. (the configuration of the atom marked "*" is racemic) According to a preferred process according to the present invention, carboxamides I are obtained by the reaction of carboxylic acid derivatives II II with amines of formula III The formation of amides is carried out by the processes known from the literature. In processes, the free carboxylic acids of the formula II 'wherein X is hydroxyl are, as a rule, previously converted to an activated carboxylic acid derivative II where X is, for example, chlorine. The activation of the carboxylic acid II 'can also preferably be carried out in situ by direct use of the carboxylic acid II' with the addition of, for example, dicyclohexylcarbodiimide, ethyl chloroformate, diethyl cyanophosphonate, triphenylphosphine / azodicarboxylic ester, 2-pyridine disulfide. / triphenylphosphine, carbonyldiimidazole, thionyl chloride, phosphorus trichloride, phosphorus pentachloride and the like. In general, for example, the carbodiimides are added in equimolar amounts based on the carboxylic acids II '.

Activation of the carboxylic acids by acyl cyanides is effected, for example, by the reaction of the carboxylic acids II 'with diethyl cyanophosphate, preferably in an inert solvent such as for example tetrahydrofuran, toluene or dichloromethane (see Tetrahedron Lett. 18 (1973) 1595-8). Activation via anhydrides is effected, for example, by the reaction of the carboxylic acids II 'with carbonic acid chlorides such as ethyl chloroformate, in general in the presence of bases, and, if appropriate, in an inert solvent such as, for example, toluene or tetrahydrofuran (see "Houben-Weyl", 4th Edition (1974), 15/1, page 28-32). The amide formation is preferably carried out in the presence of bases such as for example tertiary amines, for example, triethylamine or dimethylcyclohexylamine, alkali metal carbonates, alkali metal hydroxides, pyridine and the like. The reagents and the auxiliary base are conveniently used in equimolar quantities. A small excess of auxiliary base from 0.1 to 0.5 equivalents can be beneficial under certain circumstances. Suitable solvents are aliphatic hydrocarbons such as for example hexane and ligroin, aromatic hydrocarbons such as toluene and xylene, chlorinated hydrocarbons such as, for example, methylene chloride and 1,2-dichloroethane, ethers such as methyl tert-butyl ether and tetrahydrofuran, solvents polar aprotic, such as acetonitrile and dimethylformamide, or esters such as ethyl acetate, or mixtures thereof. The molar ratio between carboxylic acid II and amine III derivatives is generally from 0.8 to 1.5, preferably from 0.9 to 1.1. After finishing the reaction, the mixture is treated in a customary manner, for example by introducing the reaction mixture into water followed by extraction of the amide. Amines of formula III that are not yet known can be easily obtained (see Organikum (1993) Barth Verlagsgesellschaft bH Leipzig, page 509 et seq.; «Houben-Weyl», volume 15/1, pages 648-665; J. Am. Chem. Soc. 58, (1936), 1808-1811, Indian J. Chem. 10 (1972), 366). The R-isomer can be separated from the racemates of the amines III in a manner known per se, for example by fractional crystallization using optically active tartaric acid or preferably by enzyme-catalyzed esterification and subsequent hydrolysis (see for example WO-A 95/08636). The preparation of alpha-cyanocyclopropylacetic acid is described in Org. Prep. Procedure Int. 5 (1973), 25-29. Diagram 1 shows a general route of synthesis of carboxylic acids of the formula II '(see Collect, Czech, Chem. Commun. 48 (1983) 1597-1601 and J. Polym. Sci., Polym. Chem. Ed. 14 ( 1976) 2357-9). Diagram 1 go In addition, carboxylic acid derivatives of the formula I IA can be prepared according to diagram 2.

HA Die jrama 2 I IB OR JL Br. / O -OH A-JL -OR 'H Br IV Cycloalkylacetic acids of the formula IV are known wherein A has the meaning indicated in claim 1 (J. Chem. Technol. Biotechnol., Chem. Technol. 33A (1983) 109-15; NL 65 06 881; Chem. Ber 41 (1908) 2627; Chem. Ver. 35 (1902) 2688). IV cycloalkylacetic acids can be brominated in the alpha position following the protocol described in J. Am. Chem. Soc. 70 (1948) 3626-7. The treatment in the presence of C? -C6 alcochol leads directly to the corresponding ester. The subsequent bromo / cyano exchange is carried out in accordance with what is described in Synth. Commun. 23 (1993) 2323-9. Hydrolysis of the esters in the carboxylic acids IIAA 'is carried out by standard methods (Organikum 1993 Barth Verlagsgesellschaft mbH, Leipz -g, page 431 et seq.). The carboxylic acid derivatives of the formula IIB are accessible, for example, by the route illustrated in Diagram 3. Diagram 3 V VI R ^ MgHal (VH) ? B? The starting materials, acylcycloalkanes or formylcycloalkanes of the formula V, are generally accessible (see, inter alia, J. Chem. Soc, Perkin Trans. I, 6 (1994) 739-52, EP-A 725 066). React with alpha-haloacetates or C C-C6 alkyl α-cyanoacetates in a Knoevenagel reaction to provide the Michael VI systems (see Chem. Heterocycl, Compd 24 (1988) 860-4). The condensation is usually carried out with a solvent that is not miscible in water, such as for example hexane, toluene or xylene, while stirring the water formed during the reaction. For this purpose, the reaction mixture is boiled under reflux for several hours. The catalysts used are bases, for example piperidine, pyridine, ammonia or β-alanine, in the presence of an acid, for example glacial acetic acid.

A Grignard alkyl compound of the formula VII wherein R3 has the meaning provided in claim 1 and Hal is chlorine, bromine or iodine is subsequently subjected to an addition reaction with Michael systems of the formula VI to obtain saturated systems of type IIB. The reaction is carried out with inert solvents under the conditions of the reaction. Especially preferred are ethers, such as, for example, tetrahydrofuran, diethyl ether, dimethoxyethane or methyltert-butyl ether. In general terms, the temperature of the reaction is established within a range between -10 to 80 ° C, and preferably within a range between 10 and 60 ° C. In general, the Grignard VII compound is employed in an equimolar amount based on the Michael VI system. In some cases, it is advantageous to employ the Grignard compound in an excess of 0.2 to 0.5 molar equivalents. In general terms, the addition reaction is carried out with copper catalysts by the addition of 1-10 mol% of, for example, copper iodide (I). This results in a higher selectivity in the addition of 1.2 versus the addition of 1.4. Finally, the free carboxylic acids IIB 'are prepared by subjecting the corresponding esters to alkaline hydrolysis (Organikum 1993 Barth Verlagsgesellschaft mbH, Leipzig, page 431 et seq.).

A sophisticated way to obtain 2-cyano-3- (2, 2-dichlorocyclopropyl) -3-methylbutanoic acid is proposed in Diagram 4. • »Diagram 4 The preparation of 2-cyano-3, 3-dimethylpent-4-enoic acid from 3-methylbut-2-enyl cyanoacetate is described in DE-A 26 49 711 and Res. Discl. (1985) 249.55. 2-Cyano-3- (2,2-dichlorocyclopropyl) -3-methylbutanoic acid can be obtained directly by an addition reaction with dichlorocarbene, which is accessible by removing chloroform and alkali metal hydroxides by means of standard processes. To improve performance, it is convenient to protect the carboxylic acid function before the passage of • Cyclopropanation (for example, converting it to the tert-butyl ester).

The aforementioned processes allow access to derivatives and carboxylic acids II which are suitable, for example, for the preparation of the carboxamides I according to the invention. Particularly preferred embodiments of the carboxylic acid derivatives II in relation to the substituents R3, R4, A and Y correspond to the embodiments of the carboxamides I. X represents a nucleophilically exchangeable radical such as, for example, hydroxyl, C4-C4 alkoxy halogen, for example bromine or chlorine, hetaryl, such as for example imidazolyl or pyridyl, carboxylate, for example acetate or trifluoroacetate, and the like. Particularly preferred are carboxylic acid derivatives of the formula II wherein n is 1 and / or is unsubstituted or substituted cyclopropyl. In the case where n is 0, preferred carboxylic acid derivatives of the formula ILA are the derivatives wherein A is cyclopropyl on which 1 to 3 substituents may be linked, for example, chloro and / or C1-C3 alkyl. The chlorinated cyclopropyl preferably has two chlorine atoms attached thereto, and these are in the geminal position in the cyclopropane ring. Compounds I are distinguished by outstanding activity against a broad spectrum of phytopathogenic fungi, particularly from the classes of Ascomycetes, Basidiomycetes, Deuteromycetes and Phycomycetes. Some of them act systemically and can be used for crop protection for fungicides that act on foliage and soil. They are especially important to control a large number of fungi in several crops such as wheat, rye, barley, oats, rice, corn, grass, banana, cotton, soybeans, coffee, sugar cane, grapes, fruit, ornamental plants and vegetables such as cucumbers, beans, tomatoes, potatoes and cucurbits, and the seeds of these plants. Specifically, they are suitable for controlling the following plant diseases: Erysiphe graminis (powdery mold) in cereals, Erysiphe cichoracearum and Sphaerotheca fuliginea in cucurbits, Podosphera leucotricha in apples, Uncinula necator in grapes, Puccinia species in cereals, Rhizoctonia species in cotton, rice and lawns, Ustilago species in cereals and sugarcane, Venturia inaequalis (scab) in apples, Helminthosporium species in cereals, Septoria nodorum in wheat, Botrytis cinerea (gray mold) in strawberries, ornamental plants, vegetables and grapes, Cercospora arachidicola in peanuts, Pseudocercosporella herpotrichoides in wheat, oats, Pyricularia oryzae in rice, Phytophthora infestans in potatoes and tomatoes, Fusarium and Verticillium species in several plants, Plasmopara viticulture in grapes, Pseudoperonospera species (sic) in hops and cucumbers, Alternaria spices in vegetables and fruit, and Mycosphaerella species in bananas. In addition, the compounds I are suitable for controlling harmful fungi for the protection of materials (for example, wood, paper, dispersions for paint, fibers or fabrics) and for the protection of stored products. The compounds I are applied by treating the fungi or the plants, seeds, materials or soil to be protected against a fungal infection with a fungicidally reactive amount of the active ingredients. The application is carried out before or after the infection of the materials, plants or seeds by the fungus. They can be converted into customary formulations, such as solutions, emulsions, suspensions, powders, pastes and granules. The form of use depends on the intended purpose; in any way, it must guarantee a fine and uniform distribution of the compound according to the present invention. The formulations are prepared in known manner, for example, by spreading the active ingredient with solvents and / or vehicles, if desired using emulsifiers and dispersants, it being as impossible to use other organic solvents as auxiliary solvents if water is used as a diluent. The auxiliaries are essentially: solvents such as aromatics (for example xylene), chlorinated aromatics (for example chlorobenzene), paraffins (for example petroleum fractions), alcohols (for example methanol, butanol), ketones (for example cyclohexanone), amines (for example ethanolamine, dimethylformamide) and water. Vehicles such as ground natural minerals (eg kaolins, clays, talc, chalk) and ground synthetic minerals (eg highly dispersed silica, silicate); emulsifiers, such as for example nonionic and anionic emulsifiers (for example polyoxyethylene, fatty alcohol ethers, alkylsulfonates and arylsulfonates) and dispersants such as liquors of lignin-sulphite residues and methylcellulose. In general, the fungicidal compositions comprise from 0.1 to 95% by weight, preferably from 0.5 to 90% by weight of active ingredient. Depending on the nature of the desired effect, the application regimes are 0.01 to 2.0 kg of active ingredient per hectare when used for crop protection. In the treatment of seeds, amounts of 0.001 to 0.1 g, preferably 0.01 to 0.05 g, of active ingredient per kilogram of seed are generally required. When used for the protection of stored materials or products, the rate of application of the active ingredient depends on the nature of the field of application and the desired effect. For example, normal application regimes for the protection of materials are from 0.001 g to 2 kg, preferably from 0.005 g to 1 kg, of active ingredient per cubic meter of treated material. In their use as fungicides, the compositions according to the present invention can also be present together with other active ingredients such as for example with herbicides, insecticides, growth regulators, fungicides or with fertilizers. A mixture with fungicides frequently results in an extended fungicidal action spectrum. The following list of fungicides together with which the compounds according to the present invention can be used is intended to illustrate the possible combinations, but not to impose any limit: Sulfur, dithiocarbamates and their derivatives, such as, for example, iron dimethyldithiocarbamate (III), zinc dimethyldithiocarbamate, zinc ethylene bisdithiocarbamate, manganese ethylene bisdithiocarbamate, zinc manganese ethylene diamine bisdithiocarbamate, tetramethylthiuram disulfides (sic), zinc [N, N-ethylene bisdithiocarbamate] ammonia complex, ammoniacal [N, N'-propylenebisdithiocarbamate] of zinc, zinc [N, N'-propylenebisdithiocarbamate], N, N-polypropylenebis (thiocarbamoyl) disulfide; nitro derivatives, such as, for example, dinitro (1-methylheptyl) phenyl crotonate, 2-sec-butyl-4,6-dinitrophenyl 3,3-dimethylacrylate, 2-sec-butyl-4,6-dinitrophenyl isopropylcarbonate; -diisopropyl nitroisophthalate; heterocyclic substances, such as, for example, 2-heptadecyl-2-imidazoline acetate, 2,4-dichloro-6- (o-chloroanilino) -s-triazine, 0.0-diethyl phthalimidophosphothioate, 5-amino-1-bis (dimethylamino) phosphinyl] -3-phenyl-1,2,4-triazole, 2,3-dicyano-1,4-dithioanthraquinone, 2-thio-l, 3-dithiolo [4,5-b] quinoxaline, 1- methyl (butylcarbamoyl) -2-benzimidazolcarbamate, 2-methoxycarbonylaminobenzimidazole, 2- (2-furyl) benzimidazole, 2- (4-thiazolyl) benzimidazole, N- (1,1,2,2-tetrachloroethylthio) tetrahydrophthalimide, N-trichloromethyl thiotetrahydrophthalimide , N-trichloroethylthiophthalimide, N-dichlorofluoromethylthio-N ', N' -dimethyl-N-phenylsufamide, 5-ethoxy-3-trichloromethyl-l, 2,3-thiadiazole, 2-tiscianatomethylthiobenzothiazole, 1,4-dichloro-2, 5-dimethoxybenzene, 4- (2-chlorophenylhydrazono) -3-methyl-5-isoxazolone, 1-pyridin-2-thiol oxide, 8-hydroxyquinoline or its copper salt, 2,3-dihydro-5-carboxanilido-6 -methyl-l, 4-oxathiane, 2,4-dioxido-2,3-dihydro-5-carbanilido-6-methyl-1,4-oxathiane, 2-methyl-5,6-di hydro-4H-pyran-3-carboxanilide, 2-methylfuran-3-carboxanilide, 2,5-dimethylfuran-3-carboxanilide, 2,4,5-trimethylfuran-3-carboxanilide, N-cyclohexyl-2,5-dimethylfuran- 3-carboxamide, N-cyclohexyl-N-methoxy-2,5-dimethylfuran-3-carboxamide, 2-methylbenzanilide, 2-iodobenzanilide, 2,2,2-trichloroethylacetal of N-formyl-N-morpholine, piperazine-1, 4-diylbis (2,2,2-trichloroethyl) formamide, 1- (3,4-dichloroanilino) -1-formylamino-2,2,2-trichloroethane, 2,6-dimethyl-N-tridecylmorpholine or its salts, , 6-dimethyl-N-cyclododecylmorpholine or its salts, N- [3- (p-tert-butylphenyl) -2-methylpropyl] -cis-2,6-dimethylmorpholine, N- [3- (p-tert-butylphenyl) -2-methylpropyl] piperidine, 1- [2- (2, 4-dichlorophenyl) -4-ethyl-l, 3-dioxolan-2-ylethyl] -1H-1,2,4-triazole, 1- [2- (2,4-dichlorophenyl) -4-n-propyl-l, 3-dioxolan-2-ylethyl] -1H-1,2,4-triazole, N- (n-propyl) -N- (2,4, 6-trichlorophenoxyethyl) -N'-imidazolylurea, 1- (4-chlorophenoxy) -3,3-dimethyl-1- (1H-1,2,4-triazol-1-yl) -2-butanone, 1- (4 -chlorophenoxy) -3, 3-dimet il-l- (lH-1, 2,4-triazol-1-yl) -2-butanol, (2RS, 3RS) -1- [3- (2-chlorophenyl) -2- (4-fluorophenyl) oxirane- 2-ylmethyl] -1H-1,2,4-triazole, alpha- (2-chlorophenyl) -alpha- (4-chlorophenyl) -5-pyrimidinemethanol, 5-butyl-2-dimethylamino-4-hydroxy-6-methylpyrimidine , bis (p-chlorophenyl) -3-pyridinemethanol, 1,2-bis (3-ethoxycarbonyl-2-thioureido) benzene, 1,2-bis (3-methoxycarbonyl-2-thioureido) benzene, strobilurins such as E- methoximino- [alpha- (o-tolyloxy) -o-tolyl] methyl acetate, E-2-. { 2- [6- (2-Cyanophenoxy) pyrimidin-4-yloxy] phenyl} -3-methoxyacrylate, N-methyl-E-methoximino- [alpha- (2-fneoxyphenyl)] acetamide, N-methyl-E-methoximino- [alpha- (2,5- dimethylphenoxy) -o-tolyl] acetamide , anilinopyrimidines such as for example N- (4,6-dimethylpyrimidin-2-yl) aniline, N- (4-methyl-6- (1-propynyl) irimidin-2-yl) aniline, N- (4-methyl-6) -cyclopropylpyrimidin-2-yl) aniline, phenylpyrroles such as 4- (2, 2-difluoro-1,3-benzodioxol-4-yl) -pyrrole-3-carbonitrile, cinnamides such as 3- (4-chlorophenyl) -3 - (3, 4-dimethoxyphenyl) acryloylmorpholine, and various fungicides such as for example dodecylguanidine acetate, 3- [3- (3,5-dimethyl-2-oxycyclohexyl) -2-hydroxyethyl] glutarimide, hexachlorobenzene, N- (2, 6-dimethylphenyl) -N- (2-furoyl) -DL-alaninate methyl ester, DL-N- (2,6-dimethylphenyl) -N- (2'-methoxyacetyl) alanine methyl ester, N- (2, 6 -dimethylphenyl) -N-chloroacetyl-D, L-2-aminobutyrolactone, methyl ester of DL-N- (2,6-dimethylphenyl) -N- (phenylacetyl) alanine, 5-methyl-5-vinyl-3- (3 , 5-dichlorophenyl) -2,4-dioxo-l, 3-ox azolidine, 3- [3,5-dichlorophenyl (-5-methyl-5-methoxymethyl] -1,3-oxazolidin-2,4-dione, 3- (3,5-dichlorophenyl) -1-isopropylcarbamoylhydantoin, N- ( 3, 5-dichlorophenyl) -1,2-dimethylcyclopropane-1,2-dicarboximide, 2-cyano- [N- (ethylaminocarbonyl) -2-ethoximino] acetamide, 1- [2- (2,4-dichlorophenyl) pentyl) -1H-1, 2,4-triazole, 2,4-difluoro-al- (1H-1,2,4-triazolyl-1-methyl) benzydryl alcohol, N- (3-chloro-2,6-dinitro- 4, trifluoromethylphenyl) -5-trifluoromethyl-3-chloro-2-aminopyridine, 1- ((bis (4-fluorophenyl) methylsilyl) methyl) -1H-1,2,4-triazole.

The active ingredients can be applied as such in the form of their formulations or in the form of the use forms prepared from the formulations, for example, in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, dispersions in oil, pastes, powders, materials to be applied to the boleo, or granules, by means of spraying, atomization, spraying, application at boleo, or emptying. The forms of use are totally dependent on the intended purposes; in any way, they must guarantee the finest possible distribution of the active ingredients according to the invention. The concentrations of active ingredients in the ready-to-use preparations can vary within substantial ranges. Generally they are from 0.0001 to 10%, preferably from 0.01 to 1%. The active ingredients can also be used successfully in the ultra low volume (ULV) method, it being possible to apply formulations with more than 95% by weight of active ingredient, or the active ingredient can be applied without additives. The regime of application of active ingredient to control pests is from 0.1 to 2.0, preferably from 0.2 to 1.0 kg / hectare in field conditions.

Substances that are suitable for the preparation of directly sprayable solutions, emulsions, pastes or dispersions in oil are fractions of mineral oil with a medium to high boiling point, such as, for example, kerosene or diesel oil, in addition to coal tar oils and oils of plant and animal origin, aliphatic, cycloaliphatic and aromatic hydrocarbons, for example benzene, toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclohexanol, cyclohexanone, chlorobenzene, isophorone, strongly polar solvents, for example, dimethylmethylformamide, dimethyl sulfoxide, N-methylpyrrolidone or water. Aqueous forms of use can be prepared from emulsion concentrates, pastes, or wettable powders (sprayable powders, dispersions in oil) by the addition of water. To prepare emulsions, pastes or dispersions in oil, the substances, as such or dissolved in an oil or solvent can be homogenized in water by means of a wetting agent, dispersants or emulsifiers. However, it is also possible to prepare concentrates composed of active ingredient, wetting agent, dispersant or emulsifier and, if desired, solvent or oil, and these concentrates are suitable for dilution with water. Suitable surfactants are alkali metal salts, ferrous alkali metal salts and ammonium salts of lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutylnaphthalenesulfonic acid, alkylarylsulfonates, alkyl sulfates, alkyl sulfonates, fatty alcohol sulfates and fatty acids and their metal salts alkaline and ferrous alkali metal salts, glycol ether salts of sulfated fatty alcohol, condensates of naphthalene and sulfonated naphthalene derivatives with formaldehyde, condensates of naphthalene or naphthalenesulfonic acid with phenol and formaldehyde, polyoxyethylenectylphenylether, isoethoxylated ethoxylated, butylphenol, nonylphenol, ethers alkylphenyl polyglycolics, tributylphenyl polyglycol ether, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol / ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ether, ethoxylated polyoxypropylene, ether polyglycol acetal lauryl alcohol; esters of sorbitol, liquors of lignin-sulphite residues, and methylcellulose. Powders, boiling materials and particles can be prepared by mixing or concomitant grinding of the active ingredients with a solid carrier. In general, the formulations comprise from 0.01 to 95% by weight, preferably from 0.1 to 90% by weight of the active ingredients. The active ingredients are used in a purity of 90% to 100%, preferably from 95% to 100% (according to NMR spectrum). Examples of formulations are: I. 5 parts by weight of a compound according to the present invention intimately mixed with 95 parts by weight of finely divided kaolin. This provides a powder comprising 5% by weight of the active ingredient. II. 30 parts by weight of a compound according to the present invention are intimately mixed with 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 gel. silica. This provides a formulation of the active ingredient with good adhesive properties (content of active ingredient 23% by weight). III. 10 parts by weight of a compound according to the present 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 one mole of N-monoethanolamide of oleic acid, 2 parts by weight of calcium dodecylbenzenesulfonate and 2 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil (content of active ingredient: 9% by weight). IV. 20 parts by weight of a compound according to the present 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 mole of isooctylphenol and 5 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil (content of active ingredient: 16% by weight). V. 80 parts by weight of a compound according to the present invention are thoroughly mixed with 3 parts by weight of sodium diisobutylnaphthalene-a-sulfonamide, 10 parts by weight of the sodium salt of a lignosulfonic acid from waste liquor. sulfite and 7 parts by weight of silica gel powder, and the mixture is milled in a hammer mill (content of active ingredient: 80% by weight). SAW. 90 parts by weight of a compound according to the present invention are mixed with 10 parts by weight of N-methyl-alpha-pyrrolidone; this provides a solution that is suitable for use in the form of microdroplets (content of active ingredient: 90% by weight). VII. 20 parts by weight of a compound according to the present invention are dissolved in a mixture composed 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 mol of isooctylphenol and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. Emptying the solution in 100,000 parts by weight of water and distributing it therein provides an aqueous dispersion comprising 0.02% by weight of the active ingredient. VIII. 20 parts by weight of a compound according to the present invention are thoroughly mixed with 3 parts by weight of sodium diisobutyl naphthalene-sulfonate, 17 parts by weight of the sodium salt of a lignosulfonic acid from a waste liquor of sulfite and 60 parts by weight of powdered silica gel, and the mixture is milled in a martiol mill. The finely distributed mixture in 20,000 parts by weight of water provides a spray mixture comprising 0.1% by weight of the active ingredient. Granules, for example coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active ingredient to a solid carrier. Examples of solid vehicles are mineral earths, such as silica gel (silica), silicas, silica gels, silicates, talc, kaolin, clay, limestone, lime, chalk, clayey earth, loess, dolomite, diatomaceous earth, sulphate calcium, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers, for example ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and products of vegetable origin such as, for example, cereal particles, tree bark particles, wood particles and nutshell particles, cellulose powders as well as other solid vehicles. Various types of oils, either herbicides, fungicides, other pesticides, or bactericides can be added to the active ingredients, if appropriate just before use (tank mixing). These agents can be mixed with compositions according to the present invention in a weight ratio of 1:10 to 10: 1. Synthesis examples Preparation of the carboxylic acid derivatives II Example 1 1-cyano-1- (2,2-dichloro-1-methylcyclopropyl) acetic acid (compound II.1 in Table A) a) 1-bromo-l- (2, 2-dichloro-1-methylcyclopropyl) ethyl acetate and 1- (2, 2-dichloro-1-methylcyclopropyl) acetic acid (see in this context J. Chem. Technol. Biotechnol. Chem. Technol. Vol. 33A (1983), 109-15) reacted according to the protocol presented in J. Am. Chem. Soc. 70, (1948), pages 3626-7, to provide 1-bromo-l- (2, 2-dichloro- ethyl l-methylcyclopropyl) acetate. b) Ethyl 1-cyano-l- (2, 2-dichloro-l-methylcyclopropyl) acetate Bromine was exchanged for cyano by a protocol similar to Synth. Commun. 23, (1993), pages 2323-9. c) 1-cyano-l- (2,2-dichloro-l-methylcyclopropyl) acetic acid The ester was hydrolysed by refluxing 1-cyano-1- (2,2-dichloro-1-methylcyclopropyl) acetate. ethyl ester for 4 hours in a mixture of equal parts of methanol, tetrahydrofuran and a 2 N sodium hydroxide solution. For the treatment, the same volume of 2 N sodium hydroxide solution was added, and the mixture was extracted repeatedly with ether. diethyl The aqueous phase was subsequently acidified by the addition of hydrochloric acid and was also extracted with ether. Drying and concentration of this organic phase gave the title compound. Example 2 1-cyano-1- (2,2-dichlorocyclopropyl) acetic acid (compound II.2 in Table A) a) 1-bromo-1- (2,2-dichlorocyclopropyl) ethyl acetate and acid 1- ( 2, 2-dichlorocyclopropyl) acetic (see in this context NL 6506881) reacted in accordance with the protocol presented in J. Am. Chem. Soc. 70, (1948), pages 3626-7, to provide ethyl 1-bromo-1- (2, 2-dichlorocyclopropyl) acetate. b) Ethyl 1-cyano-l- (2, 2-dichlorocyclopropyl) acetate Bromine was exchanged cyano by a protocol similar to Synth. Commun. 23, (1993), pages 2323-9. c) 1-cyano-1- (2,2-dichlorocyclopropyl) acetic acid The ester was hydrolyzed by a method similar to example le). Example 3 2-Cyano-3-cyclopropylbutanoic acid (compound II.3 in Table A) a) Ethyl 2-cyano-3-cyclopropyl-2-propenoate A solution of 14 g (0.2 mol) of cyclopropylcarbaldehyde, 22.6 g (0.2 mol) of ethyl cyanoacetate, 1.4 ml of glacial acetic acid and 0.4 ml of piperidine in 200 ml of toluene was refluxed for 6 hours. After cooling, the mixture was washed with, in each case, 300 ml of 10% hydrochloric acid and water. The organic phase was dried and concentrated and the residue was subjected to vacuum distillation. This yielded 14.2 g (43% yield) of ethyl 2-cyano-3-cyclopropyl-2-propenoate (boiling point 95 ° C / 0.3 mbar). b) Ethyl 2-cyano-3-cyclopropylbutanoate 7.3 g (44 mmol) of ethyl 2-cyano-3-cyclopropyl-2-propenoate and 0.15 g of copper iodide (I) in 100 ml of dry diethyl ether were introduced. . 16.9 ml of an ether solution of 3 M methylmagnesium bromide (51 mmol) were then added dropwise at the reflux temperature and the mixture was subsequently stirred for 14 hours at room temperature. For treatment, the mixture was poured into 300 ml of ice water and stirred for 10 minutes. The aqueous phase was separated and washed with ether. The combined organic phase (sic) were washed with a sodium chloride solution, dried with sodium sulfate and concentrated. The residue was subjected to fractional distillation under vacuum. This afforded 4.9 g (61% yield) of ethyl 2-cyano-3-cyclopropylbutanoate (boiling point: 90 ° C / 2 mbar). c) 2-cyano-3-cyclopropyl-butanoic acid 39.8 g (0.22 mol) of ethyl 2-cyano-3-cyclopropylbutanoic acid were refluxed for 4 hours in a mixture of, in each case, 150 ml of methanol, tetrahydrofuran and a 2 N sodium hydroxide solution. For treatment, 200 ml of a 2 N sodium hydroxide solution was added and the mixture was extracted repeatedly with diethyl ether. The aqueous phase was subsequently acidified by the addition of hydrochloric acid and also extracted with ether. After drying and concentrating this organic phase, 29 g (86% yield) of 2-cyano-3-cyclopropylbutanoic acid were obtained. Example 4 2-Cyano-3-cyclopropyl-3-methylbutanoic acid (compound II.4 in Table A) a) Ethyl 2-cyano-3-cyclopropylbut-2-enoate A solution of 118 g (1.4 mol) of cyclopropylmethyl ketone Y 113 g (1 mol) of ethyl cyanoacetate reacted by a method similar to Example 3a) to provide 50 g (yield 29%) of ethyl 2-cyano-3-cyclopropylbut-2-enoate (boiling point 105 ° C / 6 mbar). b) ethyl 2-cyano-3-cyclopropyl-3-methylbutanoate 50 g (0.28 mol) of ethyl 2-cyano-3-cyclopropyl-3-methylprop-2-enoate and 1.5 g of copper iodide (I) reacted by a method similar to Example 3b) to provide 20 g (yield 37%) of ethyl 2-cyano-3-cyclopropyl-3-methylbutanoate (boiling point 120 ° C / 6 mbar). c) 2-cyano-3-cyclopropyl-3-methylbutanoic acid 20 g (0.1 mol) of ethyl 2-cyano-3-cyclopropyl-3-methylbutanoate were hydrolyzed by a method similar to Example 3c). This provided 13 g (yield 76%) of 2-cyano-3-cyclopropyl-3-methylbutanoic acid. Example 5 2-Cyano-3- (2,2-dichloro-l-methylcyclopropyl) butanoic acid (compound II.5 in Table A) a) Ethyl 2-cyano-3- (2, 2-dichloro-l-methylcyclopropyl) prop-2-enoate 65.8 g (0.43 mol) of (2, 2-dichloro-l) -methylcyclopropyl) carbaldehyde (see, in this context, J.

Chem. Soc., Perkin Trans. I, (1994), Vol. 6, pages 739-52) and 48.6 g (0.43 mol) of ethyl cyanoacetate reacted by a method similar to Example 3a) and gave, after distillation, 63 g (60% yield) of a pale yellow oil. Boiling point 95 ° C / 0.8 mbar, 2H NMR (in CDC13): 1.4 (t, 3H); 1.64 (s, 3H); 1.8 (d, ÍH); 2.04 (d, ÍH); 4.3 (q, 2H); 7.8 (s, ÍH))). b) Ethyl 2-cyano-3- (2, 2-dichloro-l-methylcyclopropyl) butanoate 5 g (20 mmol) of the ester obtained in Example 5a) reacted with a method similar to Example 3b) to give 5 g ( 95% yield) of 2-cyano-3- (2, Ethyl 2-dichloro-1-methylcyclopropyl) butanoate. Boiling point: 110 ° C / 0.5 mbar. c) 2-cyano-3- (2, 2-dichloro-1-methylcyclopropyl) butanoic acid 2 g (7.6 mmol) of the ester obtained in Example 5b) were hydrolysed by a method similar to Example 3c) to provide 1.7 g ( 95% yield) of the acid in the form of a brown oil. Example 6 2-Cyano-3- (2,2-dichlorocyclopropyl) -3-methyl-butanoic acid (compound II.6 in Table A) 2-cyano-3, 3-dimethylpent-4-enoic acid (see, in this context, DE 2649711 and Res. Discl. (1985), 249, 55.) was cyclopropanized according to the protocol established in J. Chem. Technol. Biotechnol., Chem. Technol. (1993), Vol. 33A, 109-15. Example 7 2-Cyano-3- (2,2-dichlorocyclopropyl) propionic acid (compound II.7 in Table A) a) Ethyl 2-cyano-3- (2, 2-dichlorocyclopropyl) propionate 4. 5 g (39 mmol) of ethyl cyanoacetate and 9.6 g (47 mmol) of 1-bromo-1- (2,2-dichlorocyclopropyl) ethane were initially charged under nitrogen in 26 ml of absolute ethanol. With stirring, 7.0 g of a 30% methanolic sodium methoxide solution were added dropwise. The mixture was heated under reflux for 2 hours. After cooling to room temperature, the mixture was stirred overnight. The methanol was evaporated and the precipitated NaBr was completely dissolved by the addition of water, with cooling to 10 ° C. The aqueous phase was extracted three times using methyl tert-butyl ether and the combined organic phases were then washed twice with water. The organic phase was dried using sodium sulphate, the solvent was removed and the crude product obtained as a residue was subjected to fractional distillation. This yielded 2.4 g (26% yield) of ethyl 2-cyano-3- (2, 2-dichlorocyclopropyl) propionate, b) 2-cyano-3- (2,2-dichlorocyclopropyl) propionic acid The hydrolysis of the ester was carried out in a manner similar to Example le).

Example 8 (1-methylcyclopentyl) cyanoacetic acid (compound II.8 in Table A) a) methyl cyanocyclopentylidinacetate In a manner similar to Example 3a), a solution of 235 g (2.8 mol) of cyclopentanone and 198 g (2 mol) of Methyl cyanoacetate reacted to give 297 g (90% yield) of methyl cyanocyclopentylidenacetate. Boiling point 92 ° C / 0.8 mbar. b) Methyl 1 (-methylcyclopentyl) cyanoacetate Similarly to Example 3b), 100 g 0.61 mol) of methyl cyanocyclopentylidinacetate and 0.7 g of copper (I) iodide reacted to provide 38 g (44% yield) of ( Methyl 1-methylcyclo-ethyl) cyanoacetate. Boiling point 85 ° C / 1.1 mbar. c) (1-methylcyclopentyl) cyanoacetic acid In a similar manner to Example 3c), 48 g (0.26 mol) of methyl (1-methylcyclopentyl) cyanoacetate were hydrolyzed. This provided 44 g (100% yield) of (1-methylcyclopentyl) cyanoacetic acid. EXAMPLE 9 2-Cyano-3-cyclopropylpentanoic acid (compound II.9 in Table A) a) Methyl 2-cyano-3-cyclopropylpent-2-enoate In a manner similar to Example 3a), a solution of 4 g (40.8 mmol ) of cyclopropyl ethyl ketone and 2.4 g (24 mmol) of methyl cyanoacetate reacted to give 0.9 g (21% yield) of methyl 2-cyano-3-cyclopropylpent-2-enoate. b) 2-cyano-3-cyclopropylpentanoate Under a nitrogen atmosphere, 1 g (5.6 mol) of ester 9a) was initially charged in 10 ml of tetrahydrofuran and 5 ml of absolute methanol. After the addition of 0.3 g (5.6 mmol) of potassium borohydride, the mixture was stirred at room temperature overnight. For the preparation, the mixture was hydrolyzed with water and acidified with 2N hydrochloric acid, and the aqueous phase was extracted with methyl tert-butyl ether. The combined organic phases were washed with water and saturated sodium chloride solution. The organic phases were dried using sodium sulfate and the solvent was removed, yielding 0.6 g (60% yield) of methyl 2-cyano-3-cyclopropylpentanoate, c) 2-cyano-3-cyclopropylpentanoic acid. Similarly to Example lc), 0.6 g of ester 9b was hydrolysed). This gave 0.54 g (98% yield) of the title compound. EXAMPLE 10 2-Cyano-3-cyclopropyl-3-methylpentanoic acid (compound 11.10 in Table A) a) Methyl 2-cyano-3-cyclopropyl-3-methylpentanoate Similar to Example 3b), 1 g (5.6 mmol) of ester 9a) reacted. This yielded 1.1 g of the crude product which was used without any further purification, b) 2-cyano-3-cyclopropyl-3-methylpentanoic acid. Similarly to Example lc), 0.5 g (2.56 mmol) of the ester 10a) was hydrolyzed. This gave 0.44 g (96% yield) of the title compound. Table A H II Preparation of the carboxamides I Example 11 N- (4'-Chlorophenyl) ethyl-1-cyclopropyl-1-cyanoacetamide (compound 1.1 in Table B) The solution of 0.62 g (5 mmol) of 1-cyano-1-cyclopropylacetic acid ( see, in this context, Org. Prep. Int. Procedure (1973), Vol. 5, pages 25-29) and 0.78 g (5 mmol) of racemic 1- (4-chlorophenyl) ethylamine in 50 ml of dichloromethane was treated with 0.5 g (5 mmol) of triethylamine. Then, 0.84 g of 93% diethyl cyanophosphonate (4.9 mmol) was added dropwise at a temperature of 10 ° C and the mixture was stirred for 12 hours at room temperature. Then, 50 ml of dichloromethane was added, the mixture was washed with, in each case, 100 ml of a 2 N sodium hydroxide solution, 5% hydrochloric acid and water. The organic phase was subsequently dried and concentrated. The residue that remained was purified by chromatography on silica gel (eluent: cyclohexane: tert-butylmethylether = 7: 3). 0.4 g (32% yield) of the diastereomer mixture of the title compound remained in the form of a solid residue with a melting point of 117-20 ° C. Example 12 N- (4 'chlorofonyl) ethyl 1-cyano-l- (2, 2-dichloro-l-methylcyclopropyl) acetamide (compound 1.4 in Table B) the reaction of 1-cyano-1- (2, 2-dichloro-l-methylcyclopropyl) acetic acid with rac-1- (4-chlorophenyl) ethylamine analogously to Example 11, gave the title compound as a mixture of diastereomers. Example 13 N- (4'-Chlorophenyl) ethyl-l-cyano-1- (2,2-dichlorocyclopropyl) -acetamide (compound 1.5 in Table B) The reaction of 1-cyano-1- (2,2-dichlorocylpropyl) acid ) acetic with racemic 1- (4-chlorophenyl) ethylamine, in a manner analogous to Example 11, gave the title compound as a mixture of diastereomers. Example 14 N- (4'-Chlorophenyl) - (R) -ethyl-2-cyano-3-cyclopropylbutanamide (compound 1.8 in Table B) The reaction of 0.46 g (3 mmol) of 2-cyano-3-cyclopropylbutanoic acid and 0.47 g (3 mmol) of Rl- (4-chlorophenyl) ethylamine by a method similar to Example 11 gave 0.65 g (yield 75%) of the title compound as a colorless resin. Example 15 N- (4'-Chlorophenyl) - (R) -ethyl-2-cyano-3-cyclopropyl-3-methyl-butanamide (compound I.10 in Table B) The reaction of 0.5 g (3 mmol) of acid 2-cyano-3-cyclopropyl-3-methylbutanoic with 0.47 g (3 mmol) of Rl- (4-chlorophenyl) ethylamine by a method similar to Example 11 gave, after purification chromatography, 0.7 g (80% yield) of the compound of the title (melting point: 103-6 ° C). Example 16 N- (4'-Chlorophenyl) - (R) -ethyl-2-cyano-3- (2,2-dichloro-l-methyl-cyclopropyl) butanamide (compound 1.12 in Table B) The reaction of 2 g ( 8.5 mmol) of 2-cyano-3- (2,2-dichloro-1-methylcyclopropyl) butanoic acid with 1.3 g (8.5 mmol) of (R) -1- (4-chlorophenyl) ethylamine by a method similar to Example 11 gave 3.1 g of the title compound (colorless resin) in the form of a mixture of diastereomers. Example 17 N- (4'-Chlorophenyl) - (R) -ethyl-2-cyano-3- (2,2-dichlorocyclopropyl) -3-methylbutanamide (compound 1.15 in Table B) The reaction of the acid obtained in Example 6 with (R) -l- (4-chlorophenyl) ethylamine by a method similar to Example 11 gives the title compound as a mixture of diastereomers. Other cycloalkylalkancarboxamides I that were prepared or can be prepared in the same manner appear in the list in Table B: Table B Table C (* = configuration in the marked atom "*", rae = racemic, R = configuration of R) EXAMPLES OF USE The fungicidal action of the compounds of the formula I against harmful fungi was demonstrated by the following greenhouse experiments: The active ingredients were formulated as a 20% emulsion in a mixture of 70% by weight of cyclohexanone, 20% by weight, weight of Nekanil® LN (Lutensol ® AP6, humidifier with emulsifying and dispersing action based on ethoxylated alkylphenols) and 10% by weight of Emulphor® EL (Emulan® EL, emulsifier based on ethoxylated fatty alcohols) and said active ingredients were diluted with water to provide the desired concentration. 1. Activity against Pyricularia oryzae (protection) Leaves of small rice plants (variety "Tai-Nong 67") in pots were treated with the aqueous preparation of the active ingredients (containing 250 ppm). After approximately 24 hours, the plants were inoculated with an aqueous spore suspension of Pyricularia oryzae. The plants that had been treated in this way were placed for 6 days in controlled environment cabinets at a temperature between 22-24 ° C and with a relative atmospheric humidity of 95 to 99%. The magnitude of the disease that had developed in the leaves was subsequently determined visually. In this test, plants that had been treated with compounds 1.7, 1.8 and 1.10 in accordance with the present invention showed a disease level of 10% or less while the disease level of the treated plants was 80%. 2. Systemic activity against Pyricularia oryzae Pregerminated rice (variety "Tai-Nong 67") was cultivated in a hydroponic system with a Hoagland solution until it reached the two-leaf stage. Then, the aqueous preparation of the active ingredient (comprising 50 ppm) was emptied near the roots. After the growth of the greenhouse plants for 5 days, the plants were inoculated with an aqueous spore suspension of Pyricularia oryzae. The plants that had been treated in this way were placed for 6 days in controlled environment cabinets at a controlled temperature between 22 and 24 ° C and at a relative atmospheric humidity of 95 to 99%. The magnitude of the disease that had developed on the leaves was subsequently determined visually. In this test, the plants that had been treated with the compounds 1.1, 12, 1.3, 1.7, 1.8 and 1.10 according to the present invention had a disease level of 15% or less, while the level of disease of the plants not treated was 80%. 3. Comparison against US 4,946,867 - systemic activity against Pyricularia oryzae The enhanced fungicidal activity of the compounds of formula I according to the present invention compared to the structurally more similar compound of the prior art (US 4,946,867) was demonstrated through of the following experiment. Compound -A (compound 9 of Table 1) known from US 4,946,867, served as a comparison compound The experiment was carried out in a manner similar to Example of Use 2 employing an aqueous active compound preparation containing 50 or 10 ppm. Active compound% leaf infection after the application of an aqueous active compound preparation containing .... ppm 50 10 (according to the invention) 1.1 (example of 40 65 comparison) A The untreated plants (controls) presented an infection of 80%.

Claims (1)

1. CLAIMS A cycloalkylalkanecarboxamide of the formula I wherein the substituents have the following meanings: A is C3-C6 cycloalkyl which may have attached thereon one to three substituents selected from the group consisting of halogen and C? -C3 alkyl; R1 is Ci-Cß alkyl or C2-C al alkenyl, it being possible for these radicals to be partially or totally halogenated and / or to have one or two of the following groups fixed thereto: C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 alkylthio -C4, C1-C4 alkoxycarbonyl, C3-C3 cycloalkyl and phenyl, it being possible for the phenyl to be partially or fully halogenated and / or to have one to three of the following radicals fixed thereon: nitro, cyano, C1-C4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 alkylthio, C 3 -C 6 cycloalkyl or heterocyclyl; R2, R3, R4 are hydrogen or, independently of this meaning, they have one of the meanings of the radical R1; n is 1; And either scyano or halogen; is phenyl, which may be fixed on it from one to three of the following groups: nitro, halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio C4, C3-C6 cycloalkyl and C?-C4 alkoxycarbonyl A cycloalkylalkanecarboxamide of the formula I where the substituents have the following meanings: A is cyclopropyl which may have attached thereon one to three substituents selected from the group consisting of halogen and C 1 -C 3 alkyl wherein the cyclopropyl group is substituted by an alkyl group at the carbon of the cyclopropene ring binding site with the rest of the -a molecule; R 1 is C 1 -C 6 alkyl or C 2 -C alkenyl, it being possible for these radicals to be partially or totally halogenated and / or to have one or two of the following groups fixed thereto: C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, alkylthio Cj.-C / C1-C4 alkoxycarbonyl, C3-C6 cycloalkyl and phenyl, it being possible for the phenyl to be partially or totally halogenated and / or to have one to three of the following radicals fixed thereon: nitro, cyano, Cf-alkyl C4, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, haloalkoxy, C 1 -C 4, C 1 -C 4 alkylthio, C 3 -C 6 cycloalkyl or heterocyclyl; R2, R3 and R4 are hydrogen or, independently of this meaning, they have one of the meanings of the radical R1; n is 0; And it is cyano or halogen; W is phenyl, which may have on it from one to three of the following groups: nitro, halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio, C3-C6 cycloalkyl and C1-C4 alkoxycarbonyl. A cycloalkylalkanecarboxamide of the formula I NB- "W wherein the substituents have the following meanings: A is C3-C6 cycloalkyl which may be affixed thereon of one to three substituents selected from the group consisting of halogen and C1-C3 alkyl; R 1 is C 1 -C 6 alkyl or C 2 -C 6 alkenyl, it being possible for these radicals to be partially or totally halogenated and / or to have one or two of the following groups fixed thereto: C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, alkylthio C1-C4, C1-C4 alkoxycarbonyl, C3-C6 cycloalkyl and phenyl, it being possible for the phenyl to be partially or fully halogenated and / or to have on it from one to three of the following radicals: nitro, cyano, C1-C4 alkyl , C1-C4 haloalkyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio, C-C6 cycloalkyl or heterocyclyl; R2, R3 and R4 are hydrogen or, independently of this meaning, they have one of the meanings of the radical R1; n is 0 or 1; And it is cyano or halogen; W is naphthyl or heteroaryl, it being possible for these radicals to have on them from one to three of the following groups: nitro, halogen, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy, haloalkoxy C1-C4 , C 1 -C 4 alkylthio, C 3 -C 6 cycloalkyl and C 1 -C 4 alkoxycarbonyl, except for the compounds of the formula I wherein n is 0 and A is cyclopentyl. A cycloalkylalkancarboxamide of the formula I according to claim 1 or according to claim 3 wherein A is cyclopropyl which may have attached thereon one to three substituents selected from the group consisting of halogen and C 1 -C 3 alkyl. 5. A cycloalkylalkanecarboxamide of the formula I according to any of claims 1-4, where A is cyclopropyl which is replaced by two chlorine atoms. 6. A cycloalkylalkanecarboxamide of the formula I according to any of claims 1 or 3-5, wherein A is cyclopropyl substituted by an alkyl group at the carbon atom of the cyclopropane ring binding site with the remainder of the molecule . 7. A cycloalkylalkanecarboxamide of the formula I according to any of claims 1-6, wherein R1 is methyl and R2, R3 and R4 are hydrogen or methyl. 8. A cycloalkylalkanecarboxamide of the formula I according to claim 3 wherein n is 1. 9. A process for the preparation of a cycloalkylalkancarboxamide of the formula I according to any of claims 1-8, comprising the reaction of a carboxylic acid derivative of the formula II wherein the radicals A, Y, R3 and R4 as well as n have the meanings set forth in claims 1, 2 or 3, and X represents a nucleophilically exchangeable radical, with an amine of the formula III, where I read radicals W, R1 and R2 have the meanings set forth in claim 1. Derivatives of carboxylic acid of the formula ILA, HA where .X represents a nucleophilically interchangeable radical; A is cyclopropyl, substituted by one to three substituents selected from the group que consisting of halogen and C 1 -C 3 alkyl, and the cyclopropyl group is substituted through an alkyl group at the carbon atom of the cyclopropane ring linking site with the rest of the molecule, and Y is cyano or halogen. 11. Carboxylic acid derivatives of the formula IIB, where X represents a nucleophilically interchangeable radical; A means C3-C5 cycloalkyl substituted by one to three substituents chosen from the group consisting of halogen and C1-C3 alkyl, and the radicals A, R3, R4 and Y have the meanings provided in claim 1. 12. A derivative of The carboxylic acid according to claim 10 or claim 11, wherein A is cyclopropyl substituted by two chlorine atoms. 13. A carboxylic acid derivative according to any of claims 11 or 12, wherein A is cyclopropyl substituted by an alkyl group at the carbon atom of the cyclopropane ring linking site with the remainder of the molecule. 14. A composition comprising such a quantity of at least one cycloalkylalkanecarboxamide of the formula I as claimed in any of claims 1-8 so as to be effective in controlling harmful fungi and at least one liquid and / or inert solid carrier. and, if appropriate, at least one surfactant. 15. A method for controlling harmful fungi, comprising the treatment of the harmful fungi, their environment or the plants, areas, materials or spaces to be kept free thereof with an effective amount of a cycloalkylalkanecarboxamide of the formula I as claimed in any of claims 1-8. 16. The use of a cycloalkylalkancarboxamide of the formula I according to any of claims 1-8 to control harmful fungi.