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    • 专利摘要:
    The present invention relates to novel cycloalkylalkanecarboxamides of formula (I) and salts useful for agriculture thereof: <Formula I> Where A is C 3 -C 6 -cycloalkyl which may have one or more substituents, Alk is straight or branched C 1 -C 6 -alkylene, R 1 is C 1 -C 6 -alkyl or C 2 -C 6 -alkenyl, which may have one or more substituents, R 2 and R 3 are hydrogen or C 1 -C 6 -alkyl or C 2 -C 6 -alkenyl, which may be partially or fully halogenated, W is a fused bicyclic ring system in which each ring has six ring atoms. The present invention also relates to fungicidal compositions containing a compound of formula (I) as a crop protection agent.
    公开号:KR20010073081A
    申请号:KR1020017002650
    申请日:1999-08-26
    公开日:2001-07-31
    发明作者:잉고 로제；프랑크 베테리히；카를 아익켄；요아킴 라인하이머；기젤라 로렌쯔；에버하르트 암머만；토마스 그로테；지크프리트 슈트라트만
    申请人:스타르크, 카르크；바스프 악티엔게젤샤프트；
    IPC主号:
    专利说明:

    Cycloalkyl Carboxylic Acid Amides, Their Production and Their Use as Fungicides in Agriculture}
    [1] The present invention relates to novel cycloalkylcarbox amides of formula (I) and salts useful for agriculture thereof.
    [2]
    [3] Where
    [4] A has one or more substituents selected from the group consisting of halogen, cyano, C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl, C 1 -C 6 -alkoxy and C 1 -C 6 -alkylthio C 3 -C 6 -cycloalkyl which may be,
    [5] Alk is straight or branched C 1 -C 6 -alkylene,
    [6] R 1 may be partially or fully halogenated and / or may be C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkoxy, C 1 -C 4 -alkylthio, C 1 -C 4 -alkoxycarbonyl, C 3 -C 6 -cycloalkyl and phenyl, wherein the phenyl can be partially or fully halogenated and / or nitro, cyano, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 1- Selected from C 4 -alkoxy, C 1 -C 4 -haloalkoxy, C 1 -C 4 -alkylthio, C 3 -C 6 -cycloalkyl, and heterocyclyl) Or C 1 -C 6 -alkyl or C 2 -C 6 -alkenyl, which may have two groups,
    [7] R 2 and R 3 are hydrogen or C 1 -C 6 -alkyl or C 2 -C 6 -alkenyl, which may be partially or fully halogenated,
    [8] W has 6 ring atoms in each ring, 1 or 2 carbon ring atoms can be replaced with nitrogen atoms, nitro, halogen, cyano, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, 1 to 3 selected from 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 It is a fused bicyclic ring system which may have a group.
    [9] EP 0 170 842 describes N-benzylcyclopropanecarboxamide derivatives and their use as agricultural fungicides. The compounds described in this patent are cyclopropylcarboxamides having a phenylalkyl group at the amide moiety and substituted by two chlorine atoms at the 2-position of the cyclopropane ring. US 4,988,734 discloses corresponding N- (R)-(1-phenylethyl) -1-alkyl-2,2-dichlorocyclopropanecarboxamide stereoisomers. US 5,034,408 also describes additional 2,2-dichlorocyclopropanecarboxamides containing a second carboxamide group at the carboxamide moiety. PCT / EP98 / 01031 also describes α-halo- and α-cyano substituted carboxamides with fungicidal action.
    [10] The fungicidal activity of known compounds is not always completely satisfactory with regard to their activity against harmful fungi such as, for example, Pyriculraia oryzae .
    [11] It is an object of the present invention to provide novel carboxamides which are active against harmful fungi.
    [12] The inventors have confirmed that this object is achieved by the cycloalkylcarboxamides of formula (I) as defined at the outset. In addition, the inventors have invented a process for preparing compounds of formula (I) and intermediates of formula (II) required for their preparation. We also invented a composition containing a compound of formula (I), a method of controlling harmful fungi using the compound of formula (I), and finally the use of a compound of formula (I) for controlling harmful fungi.
    [13] Depending on the substitution pattern, the compounds of formula (I) may contain one or more chiral centers. In this case, they exist as a mixture of enantiomers or diastereomers. The present invention provides both pure enantiomers or diastereomers and mixtures thereof.
    [14] In the definitions of the compounds of the formula (I) described at the outset, collective terms are used which denote the respective enumerated meanings of certain group members for the radicals R 1 to R 3 and A. In each case mentioned above the radical alkyl, alkylthio, alkoxy, alkoxycarbonyl and alkenyl may be straight or branched chain.
    [15] The term "partially or fully halogenated" is meant to express that the hydrogen atoms in the groups specified in this way may be partially or completely substituted by the same or different halogen atoms. In each case, the term "halogen" denotes fluorine, chlorine, bromine or iodine.
    [16] When W is a naphthyl ring in which one or two carbon ring atoms are substituted by a nitrogen atom, this is understood as quinoline, isoquinoline or naphthyridine system.
    [17] Examples of other meanings in each of the above mentioned cases are as follows:
    [18] - C 1 -C 4 - alkyl, and C 1 -C 4 - alkylthio the alkyl moiety:
    [19] Methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl and 1,1-dimethylethyl;
    [20] C 1 -C 6 -alkyl:
    [21] C 1 -C 4 -alkyl mentioned 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-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1-ethyl-1-methylpropyl and 1- Ethyl-3-methylpropyl;
    [22] C 1 -C 4 -haloalkyl:
    [23] The abovementioned C 1 -C 4 -alkyl radicals partially or completely substituted by fluorine, chlorine, bromine and / or iodine, ie chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluor Chloromethyl, 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-fluoro Ethyl, 2,2,2-trichloroethyl, pentafluoroethyl, 2-fluoropropyl, 3-fluoropropyl, 2,2-difluoropropyl, 2,3-difluoropropyl, 2-chloro Propyl, 3-chloropropyl, 2,3-dichloropropyl, 2-bromopropyl, 3-bromopropyl, 3,3,3-trifluoropropyl, 3,3,3-trichloropropyl, 2,2 , 3,3,3-penta Fluoropropyl, heptafluoropropyl, 1- (fluoromethyl) -2-fluoroethyl, 1- (chloromethyl) -2-chloroethyl, 1- (bromomethyl) -2-bromoethyl, 4 -Fluorobutyl, 4-chlorobutyl, 4-bromobutyl and nonafluorobutyl;
    [24] - C 1 -C 4 - alkoxy, and C 1 -C 4 - alkoxycarbonyl the alkoxy portion:
    [25] Methoxy, ethoxy, propoxy, 1-methylethoxy, butoxy, 1-methylpropoxy, 2-methylpropoxy and 1,1-dimethylethoxy;
    [26] C 1 -C 4 -haloalkoxy:
    [27] The abovementioned C 1 -C 4 -alkoxy radicals partially or completely substituted by fluorine, chlorine, bromine and / or iodine, ie fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorodi Fluoromethoxy, 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-bromorph Rocoxy, 2,2-difluoropropoxy, 2,3-difluoropropoxy, 2,3-dichloropropoxy, 3,3,3-trifluoropropoxy, 3,3,3-trichloro Rolopoxy, 2,2,3,3,3-pentaflu Oropropoxy, heptafluoropropoxy, 1- (fluoromethyl) -2-fluoroethoxy, 1- (chloromethyl) -2-chloroethoxy, 1- (bromomethyl) -2-bromoe Methoxy, 4-fluorobutoxy, 4-chlorobutoxy, 4-bromobutoxy and nonafluorobutoxy;
    [28] C 2 -C 6 -alkenyl:
    [29] Ethylene, prop-1-en-1-yl, prop-2-en-1-yl, 1-methylethenyl, buten-1-yl, buten-2-yl, buten-3-yl, 1- Methylprop-1-en-1-yl, 2-methylprop-1-en-1-yl, 1-methylprop-2-en-1-yl and 2-methylprop-2-ene- 1-yl, penten-1-yl, penten-2-yl, penten-3-yl, penten-4-yl, 1-methylbut-1-en-1-yl, 2-methylbut-1-ene- 1-yl, 3-methylbut-1-en-1-yl, 1-methylbut-2-en-1-yl, 2-methylbut-2-en-1-yl, 3-methylbut-2- En-1-yl, 1-methylbut-3-en-1-yl, 2-methylbut-3-en-1-yl, 3-methylbut-3-en-1-yl, 1,1-dimethyl Prop-2-en-1-yl, 1,2-dimethylprop-1-en-1-yl, 1,2-dimethylprop-2-en-1-yl, 1-ethylprop-1 -En-2-yl, 1-ethylprop-2-en-1-yl, hex-1-en-1-yl, hex-2-en-1-yl, hex-3-en-1-yl , Hex-4-en-1-yl, hex-5-en-1-yl, 1-methylpent-1-en-1-yl, 2-methylpent-1-en-1-yl, 3-methyl Pent-1-en-1-yl, 4-methylpent-1-en-1-yl, 1-methylpent-2-en-1-yl, 2-methylpent-2-en-1-yl, 3 -methyl Pent-2-en-1-yl, 4-methylpent-2-en-1-yl, 1-methylpent-3-en-1-yl, 2-methylpent-3-en-1-yl, 3 -Methylpent-3-en-1-yl, 4-methylpent-3-en-1-yl, 1-methylpent-4-en-1-yl, 2-methylpent-4-en-1-yl , 3-methylpent-4-en-1-yl, 4-methylpent-4-en-1-yl, 1,1-dimethylbut-2-en-1-yl, 1,1-dimethylbut-3 -En-1-yl, 1,2-dimethylbut-1-en-1-yl, 1,2-dimethylbut-2-en-1-yl, 1,2-dimethylbut-3-ene-1- 1,3-dimethylbut-1-en-1-yl, 1,3-dimethylbut-2-en-1-yl, 1,3-dimethylbut-3-en-1-yl, 2,2 -Dimethylbut-3-en-1-yl, 2,3-dimethylbut-1-en-1-yl, 2,3-dimethylbut-2-en-1-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, 1-ethylbut-2-en-1-yl, 1-ethylbut-3-en-1-yl, 2-ethylbut-1-en-1-yl, 2-ethylbut-2-ene-1- 1, 2-ethylbut-3-en-1-yl, 1,1,2-trimethylprop-2-en-1-yl, 1-ethyl-1-methylprop-2-en-1-yl , 1-ethyl-2-methyl Prop-1-en-1-yl and 1-ethyl-2-methylprop-2-en-1-yl;
    [30] C 3 -C 6 -cycloalkyl:
    [31] Cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, preferably cyclopropyl;
    [32] C 1 -C 6 -alkylene:
    [33] Straight or branched chain alkylene groups having 1 to 6 carbon atoms, for example methylene, 1,1-ethylene, 1,2-ethylene, 1,1-propylene, 1,2-propylene, 1,3-propylene, 1,1-butylene, 1,2-butylene, 1,3-butylene, 1,4-butylene, in particular methylene;
    [34] C 1 -C 6 -alkyl or C 2 -C 6 -alkenyl which may be partially or fully halogenated:
    [35] For the corresponding radicals mentioned in C 1 -C 6 -haloalkyl, here the alkenyl radicals, the radicals already mentioned in the definition of alkenyl are suitable.
    [36] In the present invention, cycloalkylcarboxamides of the formula (I) having the following substituents are preferred, preferred here being both effective for themselves or in combination with other definitions.
    [37] R 1 is preferably C 1 -C 6 -alkyl, such as, for example, methyl or ethyl. R 2 is preferably hydrogen or C 1 -C 6 -alkyl, for example methyl or ethyl. Especially preferred are compounds of formula I, wherein R 1 is methyl and R 2 is hydrogen.
    [38] W is preferably 1-naphthyl or 2-naphthyl.
    [39] Alk is preferably a methylene group giving a compound of the type -C (R 3 ) (R 4 )-.
    [40] In formula (I), A is preferably a cyclopropyl ring which provides a compound of formula (Ia).
    [41]
    [42] In the above formula, the substituents R 4 -R 8 are defined as follows.
    [43] R 4 is hydrogen, halogen, cyano, C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl, C 1 -C 6 -alkoxy or C 1 -C 6 -alkylthio, wherein these radicals are Partially or fully halogenated and / or C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkoxy, C 1 -C 4 -alkylthio, C 1 -C 4 -alkoxycarbonyl, C 3- May have 1 or 2 groups selected from C 6 -cycloalkyl and C 1 -C 4 -alkoxycarbonylamino,
    [44] R 5 is hydrogen, halogen, cyano, C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl, C 1 -C 6 -alkoxy or C 1 -C 6 -alkylthio, wherein these radicals are Partially or fully halogenated and / or C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkoxy, C 1 -C 4 -alkylthio, C 1 -C 4 -alkoxycarbonyl, C 3- May have 1 or 2 groups selected from C 6 -cycloalkyl and C 1 -C 4 -alkoxycarbonylamino,
    [45] R 6 is hydrogen, halogen or C 1 -C 6 -alkyl,
    [46] R 7 is hydrogen, halogen or C 1 -C 6 -alkyl,
    [47] R 8 is hydrogen, halogen or C 1 -C 6 -alkyl.
    [48] In formula (Ia), the radicals R 4 -R 8 have the following meanings, in particular in each case alone or in combination with each other.
    [49] a. R 4 is hydrogen, halogen, cyano, C 1 -C 6 -alkyl, C 1 -C 4 -alkoxycarbonylamino, for example methyl, ethyl, methoxycarbonylamino, ethoxycarbonylamino or isopropyl A compound of formula (Ia) which is oxycarbonylamino.
    [50] b. A compound of formula la wherein R 5 is hydrogen, C 1 -C 6 -alkyl, for example methyl or ethyl.
    [51] c. A compound of formula (Ia) wherein R 6 is hydrogen, C 1 -C 6 -alkyl, for example methyl or ethyl, preferably hydrogen.
    [52] d. A compound of formula la, wherein R 7 is hydrogen, chlorine or C 1 -C 6 -alkyl, for example methyl.
    [53] e. The compound of formula la, wherein R 8 is hydrogen, chlorine or C 1 -C 6 -alkyl, for example methyl.
    [54] With respect to R 4 -R 8 , the cyclopropyl ring may be mono-substituted or substituted.
    [55] Monosubstituted cyclopropyl derivatives of formula (Ia) are compounds in which a total of four radicals in R 4 -R 8 are hydrogen. Examples include compounds in which R 4 is alkyl, halogen, cyano or alkoxycarbonylamino.
    [56] Disubstituted cyclopropyl derivatives of formula (Ia) are compounds in which a total of three radicals in R 4 -R 8 are hydrogen. Examples include compounds in which R 4 is C 1 -C 6 -alkyl, halogen or cyano and R 5 is C 1 -C 6 -alkyl. Preferred disubstituted cyclopropyl derivatives are also compounds wherein R 7 and R 8 are halogen or C 1 -C 6 -alkyl.
    [57] Trisubstituted cyclopropyl derivatives of formula (Ia) are compounds in which a total of two radicals in R 4 -R 8 are hydrogen. Examples include compounds in which R 4 is C 1 -C 6 -alkyl, halogen or cyano, R 8 is halogen or C 1 -C 6 -alkyl, and R 8 is halogen or C 1 -C 6 -alkyl do.
    [58] Tetrasubstituted cyclopropyl derivatives of formula (Ia) are compounds wherein one of the radicals R 4 -R 8 is hydrogen. Examples include compounds in which R 5 or R 6 is hydrogen. Other substituents have the following meanings, for example: R 4 = C 1 -C 6 -alkyl, halogen or cyano, R 6 = C 1 -C 6 -alkyl, R 7 = halogen or C 1 -C 6 -Alkyl, R 8 = halogen or C 1 -C 6 -alkyl.
    [59] Misubstituted cyclopropyl derivatives of formula (Ia) are compounds in which none of the radicals R 4 -R 8 are hydrogen. Examples include compounds in which R 4 is C 1 -C 6 -alkyl, halogen or cyano and R 5 -R 8 is C 1 -C 6 -alkyl.
    [60] Apart from the substitution patterns mentioned above, preference is given to compounds of the formula (Ia) in which R 7 and R 8 are the same and are each halogen, in particular chlorine, or C 1 -C 6 -alkyl, in particular methyl.
    [61] If the alkylene chain Alk contains chiral carbon, it is preferably present in the R configuration.
    [62] If the compound of formula (Ia) has one or more asymmetric centers, both stereoisomeric mixtures and corresponding ethanethiomers or diastereomers are suitable for the present invention. Regarding the stereochemical arrangement of the substituents R 4 and R 5 , the compounds of the formula (Ib) are preferred.
    [63]
    [64] Especially preferred in view of their use are the compounds of formula (Ia) included in Tables 1 and 2 below.
    [65] Table 1:
    [66] Carboxamides Ic.001 to Ic.144 of formula (Ic) wherein W is a naphthyl group and R 7 and R 8 are each a methyl group (if R 1 and R 2 are different, the compounds are in racemic mixtures or in their enantiomeric form) Or a mixture thereof, wherein the carbon marked with "*" may have either an R configuration or an S configuration. Preferred is an R configuration.)
    [67]
    [68]
    [69]
    [70]
    [71]
    [72] Table 2:
    [73] The combination of R 1 -R 6 has the meaning given in the column of Table 1, W is naphthyl, and R 7 and R 8 are chlorine carboxamides Id.001 to Id.144
    [74]
    [75] According to a preferred process according to the invention, the carboxamide of formula (I) is obtained by reacting a carboxylic acid derivative of formula (II) with an amine of formula (III).
    [76] <Formula I>
    [77]
    [78] A-CO-X
    [79] H 2 N-Alk (R 1 ) (R 2 ) -W
    [80] In the above formula, X is a group that can be easily decomposed.
    [81] Amide formation reactions are carried out according to methods known from the literature. Free carboxylic acid II ', wherein X is hydroxyl, is generally first converted to an activated carboxylic acid derivative of formula II, wherein X is for example chlorine.
    [82] The activation of carboxylic acid II 'is preferably also carried out, for example, dicyclohexylcarbodiimide, ethylchloroformate, diethylcyanophosphonate, triphenylphosphine / azodicarboxylic acid ester, 2-pyridine It may also be carried out in situ by using carboxylic acid II 'directly by adding disulfide / triphenylphosphine, carbonyldiimidazole, thionyl chloride, phosphorus trichloride, phosphorus pentachloride and the like. Carbodiimide is generally added in equimolar amounts, for example, based on the carboxylic acid of formula II '.
    [83] Activation of the carboxylic acid via the acyl cyanide is carried out, for example, by reacting the carboxylic acid II 'with diethylcyanophosphonate, preferably in an inert solvent such as tetrahydrofuran, toluene or dichloromethane. [See Tetrahedron Lett. 18 (1973), 1595-8.
    [84] The activation reaction via an anhydride is carried out by, for example, reacting carboxylic acid II 'with a chloroformate, such as ethylchloroformate, generally in the presence of a base, if necessary, in an inert solvent such as toluene or tetrahydrofuran. (Houben-Weyl), 4th edition (1974), 15/1, pages 28-32).
    [85] The amide formation reaction is preferably carried out in the presence of a tertiary amine such as triethylamine or dimethylcyclohexylamine, alkali metal carbonate, alkali metal hydroxide, pyridine and the like. Starting materials and auxiliary bases are advantageously used in equimolar amounts. In certain cases it may be helpful to use a slight excess of 0.1-0.5 equivalents of auxiliary base.
    [86] Suitable solvents include 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, acetonitrile And polar aprotic solvents such as dimethylformamide, or esters such as ethyl acetate, or mixtures thereof.
    [87] The molar ratio of carboxylic acid derivative of formula II to amine of formula III is generally from 0.8 to 1.5, preferably from 0.9 to 1.1.
    [88] After the reaction is completed, the reaction mixture is worked up in a conventional manner, for example by introducing the reaction mixture into water and then extracting the amide with an organic solvent.
    [89] Carboxylic acids of formula II are known or they can be prepared by similar methods known from the literature. When A is a cyclopropyl radical, carboxylic acids can be prepared according to Scheme 1 below.
    [90]
    [91] Amines of formula III are known or can be prepared by similar methods known from the literature (Organikum (1993) Barth Verlagsgesellschaft mbH Leipzig, p. 509 ff; "Houben-Weyl", Vol. 15/1) , pp. 648-685); Indian J. Chem. 10 (1972) 366).
    [92] The R isomers may be incorporated in a known manner, for example by fractional crystallization with optically active tartaric acid, or preferably by hydrolysis following an enzyme-catalyzed esterification reaction followed by hydrolysis. It can be separated from the mate (see for example WO 95/08636).
    [93] The condensation reaction is usually carried out in a water-immiscible solvent such as hexane, toluene or xylene and the water formed during the reaction is removed. To this end, the reaction mixture is boiled for several hours under reflux.
    [94] Suitable catalysts are, for example, bases in the presence of an acid such as glacial acetic acid, for example piperidine, pyridine, ammonia or β-alanine.
    [95] X is hydroxyl, C 1 -C 4 -alkoxy, halogen, for example bromine or chlorine, hetaryl, for example imidazolyl or pyridyl, carboxylate, for example acetate or trifluoroacetate, etc. A nucleophilic substitutable radical,
    [96] Especially preferred are carboxylic acid derivatives of formula II wherein A is unsubstituted or substituted cyclopropyl,
    [97] Compounds of formula (I) have broad spectrum of phytopathogenic fungi, in particular Ascomycetes, Deuteromycetes, Phycomycetes and Basidiomycetes Has excellent activity against pathogenic fungi. Some of these act systemically and can be used for crop protection as foliar- and soil-acting fungicides.
    [98] These are especially wheat, rye, barley, oats, rice, corn, grass, bananas, cotton, soybeans, coffee, sugar cane, vines, fruits, ornamentals and cucumbers, beans, tomatoes, potatoes and gourds. A variety of crops, such as vegetables, and also seeds of these plants is important for controlling a number of fungi.
    [99] Specifically, they are suitable for controlling plant diseases such as: Erysiphe graminis (powdery mildew) of cereals , Erysiphe cichoracearum ( Pyrus ) of spaghetti Sphaerotheca fuliginea , Podosphaera leucotricha of apples, Uncinula necator of vines , Puccinia species of cereals, cotton, rice and grass Rhizoctonia species, Ustilago species of cereals and sugarcane, and Venturia inaequalis (scab) of apples, Helminthosporium of cereals ) species, wheat Seb surf Astoria Room (Septoria nodorum), strawberries, vegetables, ornamental plants and tree of Bo vine creeps Leah Tees (Botrytis cinerea: gray mold (gray mold)), Sergio peanuts Castello la la Kiddy Cola (Cercospora arachidicola), pseudo Sergio Course Four Pasteurella Herzegovina Portree wheat and barley Koh Death (Pseudocercosporella herpotrichoides), flute Temecula Rice Leah Duck chairs (Pyricularia oryzae), potatoes and pie Saratov Torah inhwe Afghanistan tomatoes Phytophthora infestans , Fusarium and Verticillium species of various plants, Plasmopara viticola of vines, Pseudoperonospora species of hops and cucumbers, vegetables And Alternaria species of fruit, and Mycosphaerella species of bananas.
    [100] The compounds of formula (I) are also suitable for the control of harmful fungi in the field of protection of materials (eg wood, paper, paint dispersions, fibers and textiles) and in the storage of articles of storage.
    [101] The compounds of formula (I) are applied by treatment to plants, seeds, substances or soils which are intended to be protected from fungal or fungal attack with a fungicidally effective amount of the active compound. Application is carried out before or after infection of the substance, plant or seed by fungi.
    [102] These can be converted to conventional preparations, for example solutions, emulsions, suspensions, powders, powders, pastes and granules. The form of use depends on the particular application desired and in any case should be such that the compounds according to the invention are finely and uniformly distributed. The formulations are prepared in a known manner, for example by emulsifying the active compound with a solvent and / or a carrier, using emulsifiers and dispersants as necessary, where other organic solvents are co-solvents when water is used as a diluent It may be used as. Suitable auxiliaries for this purpose are essentially aromatic compounds (eg xylenes), chlorinated aromatic compounds (eg chlorobenzenes), paraffins (eg mineral oil fractions), alcohols (eg methanol, butanol) ), Ketones (e.g. cyclohexanone), amines (e.g. ethanolamine, dimethylformamide) and solvents such as water, crushed natural inorganics (e.g. kaolin, clay, talc, chalk) and Carriers such as ground synthetic inorganics (eg, finely divided silica, silicates), emulsifiers such as nonionic and anionic emulsifiers (eg, polyoxyethylene fatty alcohol ethers, alkylsulfonates and arylsulfonates), and Dispersants such as lignin-sulfite waste liquor and methylcellulose.
    [103] Fungicidal compositions generally contain 0.1 to 95% by weight of active compound, preferably 0.5 to 90% by weight.
    [104] When used for crop protection, the application rate is 0.01 to 2.0 kg of active compound per ha, depending on the kind of effect desired.
    [105] When treating seed, generally an amount of 0.001 to 0.1 g, preferably 0.01 to 0.05 g of active compound per kilogram of seed is required.
    [106] When used for the protection of substances or articles of storage, the active compound application rate depends on the area of application and the kind of effect desired. Typical application rates for the protection of materials are, for example, 0.001 g to 2 kg, preferably 0.005 g to 1 kg, of active compound per m 3 of material to be treated.
    [107] The compositions according to the invention in the form of use as fungicides may also be present in combination with other active compounds, for example herbicides, insecticides, growth regulators, fungicides or else in combination with fertilizers.
    [108] In most cases, this combination provides a broader fungicidal activity spectrum.
    [109] The following list of fungicides that can be used in combination with the compounds according to the invention is presented to illustrate possible combinations and does not have any limiting meaning.
    [110] Sulfur, dithiocarbamate and derivatives thereof such as iron (III) dimethyldithiocarbamate, zinc dimethyldithiocarbamate, zinc ethylenebisdithiocarbamate, manganese ethylenebisdithiocarbamate, manganese zinc ethylene Diaminebisdithiocarbamate, tetramethylthiuram disulfide, ammonia complex of zinc (N, N-ethylenebisdithiocarbamate), ammonia complex of zinc (N, N'-propylenebisdithiocarbamate), zinc ( N, N'-propylenebisdithiocarbamate), N, N'-polypropylenebis (thiocarbamoyl) disulfide;
    [111] Nitro derivatives such as dinitro- (1-methylheptyl) phenyl crotonate, 2-tert-butyl-4,6-dinitrophenyl-3,3-dimethyl acrylate, 2-tert-butyl- 4,6-dinitrophenylisopropyl carbonate, diisopropyl 5-nitroisophthalate;
    [112] Heterocyclic compounds such as 2-heptadecyl-2-imidazoline acetate, 2,4-dinitro-6- (o-chloroanilino) -s-triazine, O, O-diethyl phthalimido Phosphonothioate, 5-amino-1- [bis (dimethylamino) phosphinyl] -3-phenyl-1,2,4-triazole, 2,3-dicyano-1,4-dithioanthraquinone, 2-thio-1,3-dithiolo [4,5-b] quinoxaline, methyl 1- (butylcarbamoyl) -2-benzimidazolecarbamate, 2-methoxycarbonylaminobenzimidazole, 2 -(Furyl- (2)) benzimidazole, 2- (thiazolyl- (4)) benzimidazole, N- (1,1,2,2-tetrachloroethylthio) tetrahydrophthalimide, N- Trichloromethylthiotetrahydrophthalimide, N-trichloromethylthioptalimide, N-dichlorofluoromethylthio-N ', N'-dimethyl-N-phenylsulfuric diamide, 5-ethoxy- 3-trichloromethyl-1,2,3-thiadiazole, 2-thiocyanatomethylthiobenzothiazole, 1,4-dichloro-2,5-dimethoxy Benzene, 4- (2-chlorophenylhydrazono) -3-methyl-5-isoxazolone, pyridine-2-thio 1-oxide, 8-hydroxyquinoline or its copper salt, 2,3-dihydro-5 -Carboxanilideo-6-methyl-1,4-oxatiin, 2,3-dihydro-5-carboxanilideo-6-methyl-1,4-oxathiine-4,4-dioxide, 2-methyl-5,6-dihydro-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, N-formyl-N-morpholine 2,2,2-trichloroethyl acetal, piperazine-1,4-diylbis- (1- (2, 2,2-trichloroethyl) formamide, 1- (3,4-dichloroanilino) -1-formylamino-2,2,2-trichloroethane, 2,6-dimethyl-N-tridecyl mor Pauline or Salts thereof, 2,6-dimethyl-N-cyclododecylmorpholine or salts thereof, 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-1,3-dioxolane- 2-ylethyl] -1H-1,2,4-triazole, 1- [2- (2,4-dichlorophenyl) -4-n-propyl-1,3-dioxolan-2-ylethyl]- 1H-1,2,4-triazole, N- (n-propyl) -N- (2,4,6-trichlorophenoxyethyl) -N'-imidazolylurea, 1- (4-chlorophenoxy C) -3,3-dimethyl-1- (1H-1,2,4-triazol-1-yl) -2-butanone, 1- (4-chlorophenoxy) -3,3-dimethyl-1 -(1H-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, α- (2-chlorophenyl) -α- (4-chlorophenyl) -5-pyrimidinmethanol, 5-butyl-2- Dimethylamino-4-hydroxy-6-methylpyrimidine, bis (p-chlorophenyl) -3-pyridinemethanol, 1,2-bis (3-ethoxycarbonyl-2-thio FIG ray) benzene, 1,2-bis- (3-methoxycarbonyl-2-thioureido) benzene;
    [113] Strobilurins, for example methyl E-methoxyimino- [α- (o-tolyloxy) -o-tolyl] acetate, methyl E-2- {2- [6- (2-cyanophenoxy C) -pyridinin-4-yloxy] -phenyl} -3-methoxy-acrylate, N-methyl E-methoxyimino- [α- (2-phenoxyphenyl)] acetamide, methyl-E- Methoxyimino- [α- (2,5-dimethylphenoxy) -o-tolyl] acetamide;
    [114] Anilinopyrimidines such as N- (4,6-dimethylpyrimidin-2-yl) aniline, N- [4-methyl-6- (1-propynyl) pyrimidin-2-yl] aniline, N -(4-methyl-6-cyclopropylpyrimidin-2-yl) aniline;
    [115] Phenylpyrrole such as 4- (2,2-difluoro-1,3-benzodioxol-4-yl) pyrrole-3-carbonitrile;
    [116] Cinnamics such as 3- (4-chlorophenyl) -3- (3,4-dimethoxy-phenyl) acryloylmorpholine; And
    [117] Various fungicides, for example dodecylguanidine acetate, 3- [3- (3,5-dimethyl-2-oxycyclohexyl) -2-hydroxyethyl] glutarimide, hexachlorobenzene, methyl N- (2 , 6-dimethylphenyl) -N- (2-furoyl) -DL-alanineate, DL-N- (2,6-dimethylphenyl) -N- (2'-methoxyacetyl) alanine methylester, 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-1,3-oxazolidine, 3- [3,5-dichlorophenyl- (5-methyl-5- Methoxymethyl] -1,3-oxazolidine-2,4-dione, 3- (3,5-dichlorophenyl) -1-isopropylcarbamoylhydantoin, N- (3,5-dichlorophenyl)- 1,2-dimethylcyclopropane-1,2-dicarboximide, 2-cyano- [N- (ethylaminocarbonyl) -2-methoxyimino] acetamide, 1- [2- (2,4 -Dichlorophenyl) pentyl] -1H-1,2,4-triazole, 2,4-difluoro-α- (1H-1,2,4- Riazolyl-1-methyl) benzhydryl 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.
    [118] The active compounds are, as such, in the form of their preparations, or in the form of applications prepared therefrom, for example, directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, powders, spray compositions, or granules. It can be applied by spraying, spraying, dispersing, spraying or watering in the form. The form of application depends entirely on the intended use and in any case they should allow the active compound according to the invention to be dispersed very finely.
    [119] The concentration of active compound in ready-to-use preparations can vary over a relatively wide range.
    [120] In general, they are 0.0001 to 10%, preferably 0.01 to 1%.
    [121] The active compounds can also be used with excellent success rates with the ultra-low-volume method (ULV), in which case formulations containing at least 95% by weight of active compound or only active compound without additives may be applied. Can be.
    [122] The application rate of the active compound for controlling the animal pests in the grazed state is 0.1 to 2.0 kg / ha, preferably 0.2 to 1.0 kg / ha.
    [123] Suitable for preparing direct sprayable solutions, emulsions, pastes or oil dispersions are petroleum fractions having medium to high boiling points, such as equivalent or diesel fuels, as well as coal tar oils and oils derived from plants or animals, aliphatic, cyclic and aromatic hydrocarbons. Benzene, toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalene or derivatives thereof, methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclohexanol, cyclohexanone, chlorobenzene, isophorone, strong polarity Solvents such as dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone and water.
    [124] Aqueous use forms can be prepared from emulsion concentrates, pastes or hydrating powders (spray powders, oil dispersions) by adding water. To prepare emulsions, pastes or oil dispersions, the compounds may be homogenized in water as such or dissolved in oils or solvents using hydrating, thickening, dispersing or emulsifying agents. However, concentrates containing active compounds, wetting agents, thickeners, dispersants or emulsifiers and, optionally, solvents or oils, which are suitable for dilution with water may also be prepared.
    [125] Suitable surfactants include alkali metal, alkaline earth metal and ammonium salts, alkylarylsulfonates, alkylsulfates, alkylsulfonates, fatty alcohol sulfates and fatty acids of lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid and dibutylnaphthalenesulfonic acid Alkali metal salts and alkaline earth metal salts, salts of sulfated fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensation products of naphthalene or naphthalene sulfonic acids with phenols and formaldehyde, polyoxyethylene octylphenol ethers , Ethoxylated isooctylphenol, octylphenol and nonylphenol, alkylphenol polyglycol ether, tributylphenyl polyglycol ether, alkylaryl polyether alcohol, isotridecyl alcohol, fatty alcohol ethylene oxide condensate, ethoxylated castor oil, poly Oxyethylene Alkyl Ether, Ethoxylated Polyoxypro Alkylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignin-sulfite waste liquid, and a methyl cellulose.
    [126] Powders, sparging compositions and powders can be prepared by mixing the active ingredients with a solid carrier or by grinding together.
    [127] The formulations generally contain from 0.01 to 95% by weight, preferably from 0.1 to 90% by weight of the active compound. The active compound is used at a purity of 90% to 100%, preferably at 95% to 100% (according to the NMR spectrum).
    [128] Examples of formulations are as follows.
    [129] I. 5 parts by weight of the compound according to the invention are thoroughly mixed with 95 parts by weight of finely divided kaolin. This yields an acid powder composition containing 5% by weight of active compound.
    [130] II. 30 parts by weight of the compound according to the invention is thoroughly mixed with a mixture of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil sprayed onto the surface of the silica gel. This gives an active compound preparation (active compound content 23% by weight) with good adhesion properties.
    [131] III. 10 parts by weight of the compound according to the invention 90 parts by weight of xylene, 6 parts by weight of 8 to 10 moles of ethylene oxide relative to 1 mole of oleic acid N-monoethanolamide, 2 parts by weight of calcium salt of dodecylbenzenesulfonic acid and castor oil It is dissolved in a mixture containing 2 parts by weight of 40 moles of adduct of 40 moles of ethylene oxide per mole (active compound content 9% by weight).
    [132] IV. 20 parts by weight of a compound according to the present invention 60 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 5 parts by weight of an additional product of 7 moles of ethylene oxide to 1 mole of isooctylphenol and 40 moles of ethylene oxide to 1 mole of castor oil Dissolve in a mixture containing 5 parts by weight of adduct (16% by weight of active compound).
    [133] V. 80 parts by weight of the compound according to the invention were mixed well with 3 parts by weight of sodium salt of diisobutylnaphthalene-α-sulfonic acid, 10 parts by weight of sodium salt of lignosulfonic acid from sulfite waste liquor, and 7 parts by weight of powdered silica gel. And grind in a hammer mill (active compound content 80% by weight).
    [134] VI. 90 parts by weight of the compound according to the invention are mixed with 10 parts by weight of N-methyl-α-pyrrolidone to give a solution suitable for use in the form of very small drops (active compound content 90% by weight).
    [135] VII. 20 parts by weight of a compound according to the present invention 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of an additional product of 7 moles of ethylene oxide to 1 mole of isooctylphenol and 40 moles of ethylene oxide to 1 mole of castor oil It is dissolved in a mixture containing 10 parts by weight of the adduct. This solution is poured into 100,000 parts by weight of water and finely dispersed therein to obtain an aqueous acid solution containing 0.02% by weight of the active compound.
    [136] VIII. 20 parts by weight of the compound according to the invention are mixed well with 3 parts by weight of sodium salt of diisobutylnaphthalene-α-sulfonic acid, 17 parts by weight of sodium salt of lignosulfonic acid from sulfite waste liquor and 60 parts by weight of powdered silica gel, and Grind in a grinder. The mixture is finely dispersed in 20,000 parts by weight of water to obtain a spray liquid containing 0.1% by weight of the active compound.
    [137] Granules such as coated granules, deposited granules and homogeneous granules can be prepared by binding the active compound to a solid carrier. Solid carriers are for example mineral soils, for example silica gel, silica, silica gel, silicates, talc, kaolin, atclay, limestone, lime, chalk, church clay, loess, clay, dolomite , Diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers, for example ammonium sulfate, ammonium phosphate, ammonium nitrate, urea and products of plant origin, for example grain flour, bark flour, wood flour And nutshell powder, cellulose powder and other solid carriers.
    [138] Various types of oils, herbicides, fungicides, other pesticides and fungicides may be added to the active compound as needed, just prior to application (tank mix). These agents can be added to the compositions according to the invention in a weight ratio of 1:10 to 10: 1.
    [139] Synthesis Example
    [140] Example 1
    [141] 1-cyano-N-[(1R) -1-naphth-2-yl-ethyl] -2,2,3,3-tetramethylcyclopropanecarboxamide
    [142] a) methyl 2-cyano-3-methylbut-2-enoate
    [143] 87 g (1.5 mol) of acetone were first charged into 100 ml of benzene. After addition of 131 g (1.33 mol) of methyl cyanoacetate, 16 g (0.28 mol) of acetic acid and 9.7 g (0.13 mol) of ammonium acetate, the mixture was heated at reflux for 10 hours on a water separator. For workup, the mixture was washed twice with 1 / 4-conc. Hydrochloric acid and water. The solution was dried over magnesium sulfate, the solvent was removed and the resulting crude product was distilled off. 108 g (55% yield) of methyl 2-cyano-3-methyl-but-2-enoate were isolated (boiling point 95 ° C./5.2 mbar).
    [144] b) methyl 1-cyano-2,2,3,3-tetramethylcyclopropane-1-carboxylate
    [145] The title compound is described in J. Org. Chem. 50 (1985), 2807-2809]: 5.6 g (50 mmol) of potassium tert-butoxide were first charged in 15 ml of dimethylsulfoxide and nitropropane 4.4 dissolved in 190 ml of dimethylsulfoxide. g (50 mmol) was added slowly dropwise. After addition of 5 g (36 mmol) of methyl 2-cyano-3-methylbut-2-enoate dissolved in 10 ml of dimethylsulfoxide, the mixture was stirred at room temperature for 40 hours. Water was added slowly to quench the reaction. The reaction mixture was extracted three times with methyl tert-butyl ether. The organic phase was dried over magnesium sulfate and ether removed to afford crude product (9 g) which was used for the next reaction without further purification.
    [146] c) 1-cyano-2,2,3,3-tetramethylcyclopropane-1-carboxylic acid
    [147] A mixture of crude methyl 1-cyano-2,2,3,3-tetramethylcyclopropyl-1-carboxylate (9 g) in the same portion of methanol, tetrahydrofuran and 2N aqueous sodium hydroxide solution (70 ml each) Hydrolysis) by refluxing for 4 hours. For workup, an equal volume of 2N aqueous sodium hydroxide solution was added and the mixture was extracted repeatedly with ether. The aqueous phase is acidified with hydrochloric acid, then extracted with methylene chloride, dried over magnesium sulfate and the solvent removed to give 1-cyano-2,2,3,3-tetramethylcyclopropyl-1-carboxylic acid as a white solid. (5.5 g, 66% yield over 2 steps).
    [148] d) 1-cyano-N-[(1R) -1-naphth-2-yl-ethyl] -2,2,3,3-tetramethylcyclopropanecarboxamide
    [149] 1-cyano-2,2,3,3-tetramethylcyclopropane-1-carboxylic acid in 50 mL of dichloromethane (Org. Prep. Proced. Int. 5, (1973), 25-29) 1.0 To a solution of g (6 mmol) and 1.03 g (6 mmol) of (1R) -1-naphth-2-ylethylamine were added 0.61 g (6 mmol) of triethylamine. Then 0.94 g (6 mmol) of diethylcyanophosphonate of 93% purity at 10 ° C. was added dropwise, and the mixture was stirred at room temperature for 12 hours. The reaction solution was concentrated using a rotary evaporator and then purified by silica gel chromatography (mobile phase: methyl tert-butyl ether: hexane = 1: 9, then 3: 7). 1.9 g (99% yield) of the title compound were isolated as a white solid at melting point 169-175 ° C.
    [150] Example 2
    [151] (1R, 3S / 1S, 3R) -2,2-dichloro-N-[(1R) -1-naphth-2-ylethyl] -1-ethyl-3-methylcyclopropanecarboxamide
    [152] a) ethyl 2,2-dichloro-1-ethyl-3-methylcyclopropane-1-carboxylate
    [153] 38 g (0.27 mol) of ethyl 2-ethylbut-2-enoate, 2.2 g (0.01 mol) of benzyltriethylammonium chloride and 57 ml of 50% strength aqueous sodium hydroxide solution were first charged to 180 ml of dichloromethane. 95 ml of chloroform were added dropwise over a period of 1 hour at 35 ° C to 40 ° C. After 5 hours of reaction time at 40 ° C. the mixture was stirred for an additional 14 hours at room temperature. The reaction solution was poured into 1.5 L of water for workup. The organic phase was separated and then the aqueous phase was extracted with dichloromethane. The combined organic phases were washed with water, dried over magnesium sulfate and concentrated. The residue (47 g) was vacuum distilled. The title compound was isolated as a colorless liquid (25.7 g, 43% yield, 71 ° C. at boiling point 2 mbar).
    [154] b) 2,2-dichloro-1-ethyl-3-methylcyclopropane-1-carboxylic acid
    [155] The ester was hydrolyzed similarly as in Example 1d). The product was isolated as an off white resin (19.7 g, 91% yield).
    [156] c) 2,2-dichloro-1-ethyl-3-methylcyclopropane-1-carbonylchloride
    [157] To produce acylchloride, 19.7 g (0.1 mol) of 2,2-dichloro-1-ethyl-3-methylcyclopropane-1-carboxylic acid is dissolved in toluene and 36.9 g (0.31 mol) thionyl chloride Was added. After 5 hours of reaction time at reflux the mixture was stirred for an additional 14 hours at room temperature. The reaction solution was concentrated using a water pump vacuum. 22 g of a brown liquid was isolated as a crude product. It was not purified before use in the next step.
    [158] d) (1R, 3S / 1S, 3R) -2,2-dichloro-N-[(1R) -1-naphth-2-yl-ethyl] -1-ethyl-3-methylcyclopropanecarboxamide
    [159] 0.62 g (2.9 mmol) of 2,2-dichloro-1-ethyl-3-methylcyclopropane-1-carbonylchloride was first charged to 20 mL of anhydrous dichloromethane. 0.5 g (2.9 mmol) of (1R) -1-naphth-2-yl-ethylamine and 0.3 g (2.9 mmol) of triethylamine were added, and then the mixture was stirred at room temperature for 16 hours. For workup, the reaction solution was diluted with the same volume of dichloromethane and washed with 2N hydrochloric acid, 2N aqueous sodium hydroxide solution and water. After drying the organic phase with magnesium sulfate and removing the solvent, the title compound was isolated as a solid (0.9 g, 81% yield). The mixture of diastereomers had a melting point of 120-135 ° C.
    [160] Example 3
    [161] (1S, 3R / 1R, 3S) -2,2-dichloro-1-ethyl-3-methylcyclopropanecarboxylic acid [(1R / 1S) -1-methyl-1-naphth-2-yl-propyl] amides
    [162] Similar to Example 1d), except that the amount of triethylamine was used twice, 0.94 g (4 mmol) of 2,2-dichloro-1-ethyl-3-methylcyclopropane-1-carbonylchloride was added to 1- Reaction with 0.86 g (4 mmol) of methyl-1-naphth-2-ylpropylamine hydrochloride gave the title compound. After purification by silica gel column chromatography (mobile phase: cyclohexane / ethylacetate gradient), the dendritic product was isolated as a mixture of diastereomers (1.1 g, 73% yield).
    [163] Physical data (NMR in CDCl 3 , in ppm) = 1 H-NMR: 0.8; 1.1; 1.2; 1.3; 1.6; 1.9; 2.2.
    [164] Example 4
    [165] (1S, 3R / 1R, 3S) -2,2-dichloro-1-ethyl-3-methylcyclopropanecarboxylic acid [(1R / 1S) -1-methyl-1-naphth-1-ylpropyl] amide
    [166] Similar to Example 1d), 0.25 g (1.1 mmol) of 2,2-dichloro-1-ethyl-3-methylcyclopropane-1-carbonylchloride was dissolved in 1-methyl-1-naphth-1-ylpropylamine hydro React with 0.23 g (1.1 mmol) chloride. After purification by silica gel column chromatography (mobile phase: cyclohexane / ethylacetate gradient) the title compound was isolated as a dendritic mixture of diastereomers (0.15 g, 38% yield). 1 H-NMR: 0.8; 1.1-1.3; 1.6; 2.0; 2.5-2.6; 6.2; 7.4; 7.6; 7.8-8.0; 8.6.
    [167] Example 5
    [168] 1-Methylcyclopropanecarboxylic acid [(1R) -1-naphth-2-yl-ethyl] amide
    [169] Similar to Example 1d), 1.5 g (15 mmol) of 1-methylcyclopropane-1-carboxylic acid was reacted with 2.6 g (15 mmol) of (1R) -1-naphth-2-ylethylamine to give the title compound. Obtained. After purification by silica gel chromatography (mobile phase: cyclohexane / ethylacetate gradient) the product was isolated as a white solid (2.9 g, 76% yield, melting point 91 ° C.).
    [170] Example 6
    [171] 1-cyano-2,2,3-trimethylcyclopropanecarboxylic acid [(1R) -1-naphth-2-ylethyl] amide
    [172] a) methyl 2-cyanobut-2-enoate
    [173] Similar to Example 1a) acetaldehyde was reacted with methyl-cyanoacetate in Knoevenagel reaction to give methyl 2-cyanobut-2-enoate.
    [174] b) methyl 1-cyano-2,2,3-trimethylcyclopropane-1-carboxylate
    [175] Similar to Example 1b), methyl 2-cyano-but-2-enoate was reacted to give methyl 1-cyano-2,2,3-trimethylcyclopropane-1-carboxylate.
    [176] c) 1-cyano-2,2,3-trimethylcyclopropane-1-carboxylic acid
    [177] Similar to Example 1c), methyl 1-cyano-2,2,3-trimethylcyclopropane-1-carboxylate is hydrolyzed to yield 1-cyano-2,2,3-trimethylcyclopropane-1-car Acid was obtained.
    [178] d) 1-cyano-2,2,3-trimethylcyclopropanecarboxylic acid [(1R) -1-naphth-2-ylethyl] amide
    [179] Similar to Example 1d), an amide of 1-cyano-2,2,3-trimethylcyclopropane-1-carboxylic acid with (1R) -1-naphth-2-ylethylamine was formed. The title compound was isolated as a yellow resin. 1 H-NMR: 1.2-1.3; 1.4; 1.6; 2.1; 5.3; 6.5; 7.4; 7.8.
    [180] Example 7
    [181] Isopropyl [1- (1R) -1-naphth-2-ylethylcarbamoyl) cyclopropyl] carbamate
    [182] a) 1-isopropoxycarbonylaminocyclopropane carboxylic acid
    [183] 0.2 g (1.98 mmol) of 1-aminocyclopropane-1-carboxylic acid were first charged into 10 ml of an aqueous 12% strength sodium hydroxide solution. After adding 0.24 g (1.98 mmol) of isopropyl chloroformate, the pH was adjusted to 9 by dropwise addition of an aqueous 12% strength aqueous sodium hydroxide solution. The mixture was stirred at rt for 14 h and then extracted twice with methyl tert-butyl ether for workup. The pH was then adjusted to 1-2 using phosphoric acid. The mixture was extracted three times with dichloromethane, the extract was dried over magnesium sulfate and the solvent removed and the title compound was isolated as a white solid (0.2 g, 54% yield).
    [184] b) isopropyl [1- (1R) -1-naphth-2-ylethylcarbamoyl) -cyclopropyl] -carbamate
    [185] To prepare the amide, 0.1 g (0.53 mmol) of 1-isopropoxycarbonylaminocyclopropane carboxylic acid was preferentially charged in 30 ml of dichloromethane. After cooling to 10 ° C., 0.5 g (0.53 mmol) of triethylamine and 0.57 g (0.53 mmol) of ethyl chloroformate were added. After stirring for 2 hours, further 0.5 g (0.53 mmol) of triethylamine and 0.9 g (0.53 mmol) of (1R) -1-naphth-2-ylethylamine were added dropwise. The mixture was stirred at rt for 16 h and then washed once with 5% strength aqueous sodium hydroxide solution, twice with 2 N hydrochloric acid and once with water. The organic phase was dried over magnesium sulfate and the solvent removed, and the residue was purified by silica gel column chromatography (mobile phase: cyclohexane: methyl tert-butyl ether = 9: 1, 6: 4, 1: 1). The title compound was isolated as an off white resin (0.14 g, 75% yield). 1 H-NMR: 0.8-1.0; 1.2; 1.4; 1.6; 4.9-5.1; 5.3; 6.8; 7.5; 7.8.
    [186] Example 8
    [187] 3- (2,2-dichlorovinyl) -2,2-dimethylcyclopropanecarboxylic acid [(1R) -1-naphth-2-ylethylamide]
    [188] Starting materials are described in J. Org. Chem. 53 (16) (1988), 3843-3845. 0.47 g (2.24 mmol) of 3- (2,2-dichlorovinyl) -2,2-dimethylcyclopropanoic acid was dissolved in 50 mL of anhydrous methylene chloride and 0.22 g (2.24 mmol) of triethylamine and (1R) -1 -Mixed with 0.38 g (2.24 mmol) of naphth-2-ylethylamine. The reaction flask was cooled to 0 ° C. and then 0.33 g (2.02 mmol) of ethylcyanoacetate in 93% purity was added.
    [189] After the addition was complete, the ice bath was removed and the mixture was stirred overnight. The reaction solution was washed successively once more with 2 N aqueous sodium hydroxide solution, water, 2 N hydrochloric acid, water, 2 N aqueous sodium hydroxide solution and finally with water. The organic phase was dried over magnesium sulfate, the solvent was removed, and the product was separated into a yellow resin by silica gel column chromatography (mobile phase: cyclohexane / ethyl acetate 9.5: 0.5, then 7: 3). The title compound 3- (2,2-dichlorovinyl) -2,2-dimethylcyclopropanecarboxylic acid [(1R) -1-naphth-2-ylethyl] amide was likewise used since diastereomeric starting materials were used. Obtained as a mixture of diastereomers (0.5 g, 62% yield).
    [190] Physical data ( 1 H-NMR, CDCl 3 , in ppm): 1.1-1.3; 1.4; 1.6; 1.9; 2.3; 5.3; 5.6; 5.8; 6.4; 7.4; 7.7-7.9.
    [191] Example 9
    [192] 3- (2-Chloro-3,3,3-trifluoropropenyl) -2,2-dimethylcyclopropanecarboxylic acid [(1R) -1-naphth-2-yl-ethyl] amide, (E ) -Isomer
    [193] According to patent JP 62/116531 the starting material was obtained as a mixture of diastereomers.
    [194] 0.54 g (2.24 mmol) of (E) -3- (2-chloro-3,3,3-trifluoropropenyl) -2,2-dimethylcyclopropane carboxylic acid was dissolved in 50 ml of anhydrous methylene chloride and 0.22 g (2.24 mmol) ethylamine and 0.38 g (2.24 mmol) (1R) -1-naphth-2-ylethylamine were mixed. The reaction flask was cooled to 0 ° C. and then 0.33 g (2.02 mmol) of ethylcyanoacetate in 93% purity was added.
    [195] After the addition was complete, the ice bath was removed and the mixture was stirred overnight. For workup the reaction solution was washed once more with 2N aqueous sodium hydroxide solution, then with water, 2N hydrochloric acid, water, 2N aqueous sodium hydroxide solution and finally with water. The organic phase was dried over magnesium sulfate, the solvent was removed and the product was separated by separation by silica gel column chromatography (mobile phase: cyclohexane / ethyl acetate 9.5: 0.5, then 7: 3). This gave 0.7 g (79% yield) of the diastereomer title compound as yellow crystals [melting point 75 ° C.-77 ° C.].
    [196] Example 10
    [197] 3- (2-Chloro-3,3,3-trifluoropropenyl) -2,2-dimethylcyclopropanecarboxylic acid [(1R) -1-naphth-2-yl-ethyl] amide, (Z ) -Isomer
    [198] According to patent JP 62/116531 the starting material was obtained as a mixture of diastereomers.
    [199] 0.54 g (2.24 mmol) of (E) -3- (2-chloro-3,3,3-trifluoropropenyl) -2,2-dimethylcyclopropane carboxylic acid was dissolved in 50 ml of anhydrous methylene chloride and 0.22 g (2.24 mmol) ethylamine and 0.38 g (2.24 mmol) (1R) -1-naphth-2-ylethylamine were mixed. The reaction flask was cooled to 0 ° C. and then 0.33 g (2.02 mmol) of ethylcyanoacetate in 93% purity was added.
    [200] After the addition was complete, the ice bath was removed and the mixture was stirred overnight. For workup, the reaction solution was washed successively with 2 N aqueous sodium hydroxide solution, followed by water, 2 N hydrochloric acid, water, 2 N aqueous sodium hydroxide solution and finally water. The organic phase was dried over magnesium sulfate, the solvent was removed, and the product was separated by purification by silica gel column chromatography (mobile phase: cyclohexane / ethylacetate = 9.5: 0.5, then 7: 2). This gave 0.6 g (68% yield) of the diastereomer title compound as a yellow resin.
    [201] Physical data ( 1 H, CDCl 3 , ppm): 1.2-1.3; 1.4; 1.5-1.6; 2.5; 5.3; 5.9; 6.1; 7.4; 7.7-7.9.
    [202] Example 11
    [203] Use Example
    [204] The fungicidal activity of the compounds of formula I against harmful fungi has been demonstrated by the following greenhouse experiments.
    [205] Active ingredient: 70% by weight of cyclohexanone, Necanyl (Nekanil®) LN (Lutensol® AP6, 20% by weight of an emulsifying and dispersing agent based on an ethoxylated alkylphenol) and an emulsion (Emulphor® EL) (Emulan® EL, an emulsifier based on ethoxylated fatty alcohols) was formulated as a 20% strength emulsion in a 10% by weight mixture and diluted with water to give the desired concentration. .
    [206] 1.Activity (protective action) against Pyricularia oryzae
    [207] Leaves of rice seedlings (cultivar "Tai-Nong 67") grown in pots were treated with an aqueous formulation of the active ingredient (content 250 ppm). After about 24 hours the plants were inoculated with an aqueous spore suspension of Pyricularia oryzae . Plants treated in this manner were placed in a controlled environment cabinet at 22-24 ° C. and 95-99% relative humidity for 6 days. Subsequently, the degree of disease expressed in the leaves was visually measured.
    [208] In this test, plants treated with the compounds according to the invention showed low disease levels, while disease levels of untreated plants were 80%.
    [209] 2. Systemic Activity on Pyricularia oryzae
    [210] Pre-germinated rice (cultivar “Tai-Nong 67”) was grown in hydroponic cultivation system using a Hoagland solution until reaching the two-leaf stage. Thereafter, an aqueous formulation of the active ingredient (content 50 ppm) was poured by the root. After growing the plants in the greenhouse for an additional 5 days, they were inoculated with an aqueous spore suspension of Pyricularia oryzae . Plants treated in this manner were placed in a controlled environment cabinet at 22-24 ° C. and 95-99% relative humidity for 6 days. Subsequently, the degree of disease expressed in the leaves was visually measured.
    [211] In this test, plants treated with the compounds according to the invention showed low disease levels, while disease levels of untreated plants were 80%.
    权利要求:
    Claims (13)
    [1" claim-type="Currently amended] Cycloalkylcarboxamides of formula (I) and salts useful for agriculture thereof.
    <Formula I>

    Where
    A has one or more substituents selected from the group consisting of halogen, cyano, C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl, C 1 -C 6 -alkoxy and C 1 -C 6 -alkylthio C 3 -C 6 -cycloalkyl which may be,
    Alk is straight or branched C 1 -C 6 -alkylene,
    R 1 may be partially or fully halogenated and / or may be C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkoxy, C 1 -C 4 -alkylthio, C 1 -C 4 -alkoxycarbonyl, C 3 -C 6 -cycloalkyl and phenyl, wherein the phenyl can be partially or fully halogenated and / or nitro, cyano, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 1- May have 1 to 3 radicals selected from the group consisting of C 4 -alkoxy, C 1 -C 4 -haloalkoxy, C 1 -C 4 -alkylthio, C 3 -C 6 -cycloalkyl and heterocyclyl) C 1 -C 6 -alkyl or C 2 -C 6 -alkenyl, which may have one or two groups selected from the group consisting of
    R 2 and R 3 are hydrogen or C 1 -C 6 -alkyl or C 2 -C 6 -alkenyl, which may be partially or fully halogenated,
    W is a fused bicyclic ring system in which each ring has six ring atoms, in which one or two carbon ring atoms can be replaced with nitrogen atoms, nitro, halogen, cyano, C 1 -C 4 -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 It may have 1 to 3 groups selected from the group consisting of alkoxycarbonyl.
    [2" claim-type="Currently amended] The cycloalkylcarboxamide according to claim 1, represented by the following general formula (Ia).
    <Formula Ia>

    Where
    R 4 is hydrogen, halogen, cyano, C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl, C 1 -C 6 -alkoxy or C 1 -C 6 -alkylthio, the radicals being partially Or fully halogenated and / or C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkoxy, C 1 -C 4 -alkylthio, C 1 -C 4 -alkoxycarbonyl, C 3 -C 6 May have 1 or 2 groups selected from the group consisting of -cycloalkyl and C 1 -C 4 -alkoxycarbonylamino,
    R 5 is hydrogen, halogen, cyano, C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl, C 1 -C 6 -alkoxy or C 1 -C 6 -alkylthio, the radicals being partially Or fully halogenated and / or C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkoxy, C 1 -C 4 -alkylthio, C 1 -C 4 -alkoxycarbonyl, C 3 -C 6 May have 1 or 2 groups selected from the group consisting of -cycloalkyl and C 1 -C 4 -alkoxycarbonylamino,
    R 6 is hydrogen, halogen or C 1 -C 6 -alkyl,
    R 7 is hydrogen, halogen or C 1 -C 6 -alkyl,
    R 8 is hydrogen, halogen or C 1 -C 6 -alkyl.
    [3" claim-type="Currently amended] The cycloalkylcarboxamide of formula Ia according to claim 2, wherein the cyclopropyl ring can have 1 to 5 substituents R 4 -R 8 selected from the radical group consisting of halogen, cyano and C 1 -C 3 -alkyl. .
    [4" claim-type="Currently amended] 3. A compound according to claim 2 wherein R 4 is halogen, cyano, C 1 -C 6 -alkyl, C 1 -C 4 -alkoxycarbonylamino, C 1 -C 4 -alkoxy or C 1 -C 4 -alkylthio Cycloalkylcarboxamides.
    [5" claim-type="Currently amended] 5. The cycloalkylcarboxamide of claim 2 wherein R 5 is hydrogen or C 1 -C 6 -alkyl.
    [6" claim-type="Currently amended] 6. The cycloalkylcarboxamide according to claim 2, wherein R 6 is hydrogen or C 1 -C 6 -alkyl. 7.
    [7" claim-type="Currently amended] The cycloalkylcarboxamide of any one of claims 2 to 6 wherein R 7 is hydrogen, chlorine or C 1 -C 6 -alkyl.
    [8" claim-type="Currently amended] 8. The cycloalkylcarboxamide of claim 2 wherein R 8 is hydrogen, chlorine or C 1 -C 6 -alkyl.
    [9" claim-type="Currently amended] The cycloalkylcarboxamide of claim 1, wherein R 1 is C 1 -C 6 -alkyl and R 2 is hydrogen or C 1 -C 6 -alkyl.
    [10" claim-type="Currently amended] The cycloalkylcarboxamide according to any one of claims 1 to 9, wherein Alk is a methylene group.
    [11" claim-type="Currently amended] 11. A fungicidally effective amount of at least one cycloalkylcarboxamide of formula (I) according to any one of claims 1 to 10, together with an inert liquid and / or solid carrier and, if necessary, at least one surfactant. Composition.
    [12" claim-type="Currently amended] A method for controlling harmful fungi by treating an effective amount of the cycloalkylcarboxamides of formula I according to any one of claims 1 to 10 with harmful fungi, their habitats or the plants, regions, substances or spaces from which they are to be removed. .
    [13" claim-type="Currently amended] Use for controlling harmful fungi of the cycloalkylcarboxamides of formula I according to any one of claims 1 to 10.
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    IL141533D0|2002-03-10|
    CN1320115A|2001-10-31|
    DE59903673D1|2003-01-16|
    AU5740999A|2000-03-21|
    BR9913361A|2001-05-22|
    EP1107946A2|2001-06-20|
    WO2000012465A3|2000-06-22|
    EP1107946B1|2002-12-04|
    WO2000012465A2|2000-03-09|
    HU0103891A2|2002-03-28|
    IL141533A|2004-12-15|
    AT228996T|2002-12-15|
    US6441044B1|2002-08-27|
    HU0103891A3|2003-04-28|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    1998-09-01|Priority to DE19839690
    1998-09-01|Priority to DE19839690.2
    1999-08-26|Application filed by 스타르크, 카르크, 바스프 악티엔게젤샤프트
    1999-08-26|Priority to PCT/EP1999/006251
    2001-07-31|Publication of KR20010073081A
    优先权:
    申请号 | 申请日 | 专利标题
    DE19839690|1998-09-01|
    DE19839690.2|1998-09-01|
    PCT/EP1999/006251|WO2000012465A2|1998-09-01|1999-08-26|Cycloalkyl carboxylic acid amides, their production and their use as fungicides in agriculture|
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