MXPA02002470A - Cyclopropane carboxylic acid amides, the production and the use thereof. - Google Patents

Abstract

The invention relates to cyclopropane carboxylic acid amides of general formula (I), wherein the substituents have the following meaning: R1 represents substituted or unsubstituted C1C6 alkyl or C2C6 alkenyl groups, R2 represents hydrogen or independently thereof one of the meanings of R1, R3 represents hydrogen or C1C6 alkyl; Y represents cyano or halogen, and W represents a substituted or unsubstituted phenyl. The invention also relates to the optically active forms and agriculturally useful salts thereof.

Description

• ^ j__j AMIDAS DE CICLOPROPANO ACIDOS CARBOXILICOS SU PRODUCTION AND USE The present invention relates to the novel 5-cyclopropancarboxamides of the formula I: 10 where: R is C 1 -C 6 alkyl or C 2 -C 6 alkenyl, where these radicals can be partially or completely halogenated and / or can carry one or two of the following groups: C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, alkylthio C1-C4, C3-C6-C6-C6-alkoxycarbonyl, and phenyl, wherein the phenyl ring may be partially or completely halogenated and / or may carry from one to three of the following radicals: nitro, cyano, C1-C4, 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 R is hydrogen or has one of the meanings of the radical R independently of the meaning of R R "is hydrogen or Ci-Cß alkyl; And it is cyano or halogen; W is phenyl, where this radical can carry from one to three of the following groups: nitro, halogen, cyano, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, alkylthio C1-C4, C3-C6 cycloalkyl and C1-C4 alkoxycarbonyl and its forms with optical activity and the salts useful in agriculture, except for the compound N- [1- (4-chlorophenyl) ethyl] -1- cyano-2,2,3,3-tetramethylcyclopropanecarboxamide in racemic form.

Carboxamides substituted with a-halo and a-cyano to control deleterious fungi, in particular to control Pyricularia oryzae, have already been described in the Literature (JP-A 57 185202, JP-A 57 188552, JP-A 57 188551, JP-A 58 029751, JP-A 58 029752, WO 95/31432, JP-A 07 206608, JP-A 07 330511, JP -A 08 012508, JP-A 07 330511, JP-A 08 012508 and US 4,946,867). J. Pestic. Sci. 12, (1987), 79-84, summarize publications related to the substituted a-halo carboxamides described above. In addition, this article attempts to establish the structure-activity quantitative relationships for this class of fungicides.

JP 89-55786 (JP 2,639,099) mentions a cyclopropancarboxamide, N- [1- (4-chlorophenyl) ethyl] -1-cyano-2,2,3,3-tetramethylcyclopropanecarboxamide (racemate). Compounds with optical activity (enantiomers) have not been described.

JP 09-194465 mentions a plurality of cyclopropancarboxamides, including N- [l-benzothiazol-2-ylthyl] -l-cyano-2,2,3, 3-tetramethylcyclopropanecarboxamide.

The fungal properties of the compounds of the prior art are not completely satisfactory with respect to their activity against harmful fungi such as, for example, Pyricularia oryzae.

An object of the present invention is to offer novel carboxamides that are more effective against harmful fungi, such as Pyricularia oryzae. Another objective of the invention is to improve the selectivity in addition to the efficiency, thus reducing the damage to the plants.

We have found that this goal is achieved by the novel cycloalkylalkanecarboxamides I defined at the beginning. Surprisingly, the compounds are taken through the roots of the plants, and these unfold their fungicidal action being taken by the plants without showing phytotoxic effects of the phenethylcarboxamides. Due to the fact that these have systemic action and are taken by the roots, the active compounds according to the invention are particularly suitable for application in the seedling boxes. In addition, we have found processes to prepare the compounds I and the intermediates of the formula II necessary for their preparation. We have found compositions containing the compounds I, the methods for controlling the harmful fungi using the compounds I and, finally, the use of the compounds I for controlling harmful fungi.

The compounds of the formula I contain a chiral center. The invention provides the pure enantiomers and their mixtures and racemates.

In the definition of the compounds I which are given at the beginning, collective terms were used for the radicals R 1, R 2, R 3 and Z which represent individual enumerations of the members of the individual groups. The alkyl, alkylthio, alkoxy, alkoxycarbonyl and alkenyl radicals can be straight chain or branched.

The term "partially or completely halogenated" means that the hydrogen atoms in the groups so characterized may be partially or completely substituted by identical or different halogen atoms. The term "halogen" in each case represents fluorine, chlorine, bromine or iodine.

Examples of other meanings are: C 1 -C 4 alkyl, and C 1 -C 4 alkylthio alkyl portions: methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl and 1,1-dimethyl-ethyl; - C 1 -C 4 alkyl: C 1 -C 4 alkyl as already mentioned 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; - haloalkyl of C? ~ C4: a C 1 -C 4 alkyl radical as already mentioned that is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, ie 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-pentafluoropropyl, heptafluoropropyl, 1- (fluoromethyl) ) -2-fluoroethyl, 1- (chloromethyl) -2,5-chloroethyl, 1- (bromomethyl) -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 radical C 1 -C 4 alkoxy radical as already mentioned that is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, ie for example, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorodifluoromethoxy, bromodifluoromethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2- 20-bromomethoxy, 2-iodoethoxy, 2,2-difluoroethoxy, 2,2,2-tpfluoroethoxy, 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, 2-25 bromopropoxy, 3-bromopropoxy, 2, 2- difluoropropoxy, *! «« «__% > _! --_-_. ffCJ ^? Á »^ 3í * if.? á ^? iii? ¿., e? a.í ^ St? S zk i? m &u ..-- ^ '? 'fjT.' 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-bromoethoxy, 4-fluorobutoxy, 4-chlorobutoxy, 4-bromobutoxy and nonafluorobutoxy; - C?-C6 alkenyl: ethylene, prop-1-en-l-yl, prop-2-en-1-yl, 1-methylethenyl, buten-1-yl, buten-2-yl, buten-3- ilo, 1-methylprop-l-en-l-yl, 2-methylprop-l-en-1-yl, l-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-1-en-1-yl, 2-methylbut-1-en-1-yl, 3- methylbut-l-en-l-yl, l-methylbut-2-en-l-yl, 2- methylbut-2-en-l-yl, 3-methylbut-2-en-l-yl, 1- methylbutyl- 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-1-en-l-yl, 1,2-dimethylprop-2-en-l-yl, 1-ethylprop-1-en-2-yl, l-ethylprop-2-en-1-yl, hex- l-en-1-yl, hex-2-en-l-yl, hex-3-en-l-yl, hex-4-en-l-yl, hex-5-en-l-yl, 1- methylpent-l-en-l-yl, 2-methylpent-l-en-l-yl, 3-methylpent-l-en-l-yl, 4-methylpent-l-en-l-yl, l-methylpent- 2-en-l-yl, 2-methylpent-2-en-l-yl, 3-methylpent-2-en-l-yl, 4-methylpent-2-en-l-yl, 1- -jf "f • ^ f ^ J Methylpent-3-en-l-yl, 2-methylpent-3-en-l-yl, 3-methylpent-3-en-l-yl, 4-methylpent-3-en -l-yl, 1- methylpent-4-en-l-yl, 2-methylpent-4-en-l-yl, 3-methylpent-4-en-l-yl, 4-methylpent-4-en-l -yl, 1,1-dimethylbut-2-en-l-yl, 1, l-dimethylbut-3-en-l-yl, 1,2-dimethylbut-1-en-l-yl, 1,2-dimethylbut -2-en-l-yl, 1,2-dimethylbut-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 -in-l-yl, 2, 3-dimethylbut-3-en-l-yl, 3,3-dimethylbut-1-en-l-yl, 3, 3-dimethylbut-2-en-l-yl, 1 ethylbut-1-en-l-yl, l-ethylbut-2-en-l-yl, l-ethylbut-3-en-l-yl, 2-etyl-l-l-en-l-yl, 2 -ethylbut-2-en-l-yl, 2-ethylbut-3-en-l-yl, 1,1, 2-trimethylprop-2-en-l-yl, l-ethyl-l-methylprop-2-en -l-yl, l-ethyl-2-methylprop-l-en-l-yl and l-ethyl-2-methylprop-2-en-l-yl; - C3-C6 cycloalkyl: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl.

In view of the fungicidal action against harmful fungi such as, for example, Pyricularia oryzae, cyclopropancarboxamides I with the following substituents are preferred, preference being given in each case alone or in combination: The carbon atom carrying the groups R 1 and R 2 is preferably in the R configuration. The preferred cyclopropancarboxamides I are those where R 1 is methyl and R 2 is methyl or hydrogen; especially preferred are compounds I wherein R is methyl R is hydrogen. R is preferably hydrogen Other preferred cyclopropancarboxamides of the formula I are those in which W is unsubstituted or substituted phenyl which is substituted in particular in the 4-position or in the 2-position and 4-position, preferably by alkyl, alkoxy, nitro and / or halogen. It is very particularly preferred to substitute the phenyl ring in the 2, 4 position, in particular by halogen, and in this case preferably chlorine.

In addition, preference is given to a-chloro- or a-bromocyclopropanecarboxamides I (Y = bromine or chlorine). Particular preference is given to a-cyanocyclopropanecarboxamides I (Y = cyano). Among these, a-cyanocyclopentylcarboxamides I (Y = cyano, n = 5) are particularly preferred. '' '- - - "^> .____" * __-______ < ^ f.l "-fr-i ^^ According to a process that is preferred according to the invention, carboxamides I: they are obtained by reacting carboxylic acid II derivatives: with amines of formula III In the synthesis of novel compounds of type I, using the procedures of the literature (K. Annen et al, Chem. Ver. 111 (1978), 3094-3104; N. Ono et al., J. Org. Chem. 50 81985), 2807-2809) the methyl ester of the intermediate l-cyano-2, 2,3,3-tetramethylcyclopropanecarboxylic acid II was prepared from the .AÉJÉtriMf _-? If "•" '•' - * i - • + ^ ~ "____d___i principle. Hydrolysis and subsequent amidation using phenethylamines III gives the objective compounds I.

The formation of the amide is carried out by known processes of the literature. In processes, the free carboxylic acids of formula II 'wherein X is hydroxyl are usually pre-converted into an activated carboxylic acid II derivative where X is, for example, chlorine.

The activation of the carboxylic acids II 'can preferably also be carried out in situ by the direct use of the carboxylic acids II' with the addition of, for example, dicyclohexylcarbodiimide, ethyl chloroformate, diethyl cyanophosphonate, triphenylphosphine / azodicarboxylic ester, sodium disulfide. 2- pyridine / triphenylphosphine, carbonyldiimidazole, thionyl chloride, phosphorus trichloride, phosphorus pentachloride and the like. In general, the carbodiimides, for example, are added in equimolar quantities based on the carboxylic acids II '.

Activation of the carboxylic acids via the acyl cyanides is carried out, for example, by reacting the carboxylic acids II 'with cyanophosphonate of diethyl, preferably in an inert solvent, such as tetrahydrofuran, toluene or dichloromethane (see Tetrahedron Lett, 18 (1973) 1595-8).

The activation through the anhydrides is effected, for example, by reacting the carboxylic acids II 'with chloroformates, such as ethyl chloroformate, generally in the presence of bases and, if appropriate, in an inert solvent such as toluene or tetrahydrofuran. (See "Houben-Weyl", 4th ed. (1974), 15/1 pages 28-32).

The formation of the amide is preferably carried out in the presence of bases, such as tertiary amines, for example, triethylamine or dimethylcyclohexylamine, alkali metal carbonates, alkali metal hydroxides, pyridine and the like. The reactants and the auxiliary base are conveniently employed in equimolar amounts. A slight excess of the auxiliary base of 0.1- 0.5 equivalents may be beneficial under certain circumstances.

Suitable solvents are aliphatic hydrocarbons such as hexane and ligroin, aromatic hydrocarbons such as toluene and xylene, chlorinated hydrocarbons such as methylene and 1,2-dichloroethane, ethers such as methyl terbutyl ether and tetrahydrofuran, polar aprotic solvents such as acetonitrile and dimethylformamide, or esters such as ethyl acetate, or mixtures thereof.

The molar ratio of the carboxylic acid derivatives II to the amine III in general is from 0.8 to 1.5 and, preferably, from 0.9 to 1.1.

After the reaction is complete, the mixture is subjected to the usual treatment, for example, by introducing the reaction mixture into water, followed by extraction of the amide.

Amines of formula III which are not already known can be obtained easily (see Organikum 81993) Barth Verlagsgesellschaft mbH Leipzig, p. 509 ff .; "Houben-Weyl", Volume 15/1, pages 648-665; J. Am. Chem. Soc. 58, (1936), 1808-181, Indian J. Chem. 10 (1972) 366).

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

Finally, the free carboxylic acids IIB 'are prepared by subjecting the corresponding esters to alkaline hydrolysis (Organikum 1993, Barth Verlagsgesellschaft mbH, Leipzig, p 431ff.).

The aforementioned processes allow access to the carboxylic acid derivatives II which are suitable, for example, for preparing the carboxamides I according to the invention.

Particularly preferred embodiments of the carboxylic acid derivatives II with respect to the substituents R 3, R 4 A and Y correspond to those of the carboxamides I.

X is a nucleophilically exchangeable radical, such as hydroxyl, C? -C4 alkoxy, halogen, for example bromine or chlorine, hetaryl for example imidazolyl or pyridyl, carboxylate, for example, acetate or trifluoroacetate and the like.

Particular preference is given to the carboxylic acid derivatives of the formula II in which the i.á?.? ... I? -, - .. i ... ». ___-. , '.. »5l____ < | -_jl _ ». 4_, carbon atoms of the linking ring carries a methyl group.

Compounds I have outstanding activity against a broad spectrum of phytopathogenic fungi, in particular from the classes of ascomycetes, deuteromycetes, phycomycetes and basidiomycetes. Some of these act systemically and can be used to protect crops as fungicides with leaves and soil action.

These are especially important for controlling a large number of fungi in a variety of crop plants such as wheat, barley, rye, oats, rice, corn, grasses, bananas, cotton, soybeans, coffee, sugarcane, vines, fruit species, Ornamentals and vegetables such as cucumbers, beans, tomatoes, potatoes and cucurbits, and on the seeds of these plants.

Specifically, these are suitable for controlling the following plant diseases: Erysiphe graminis (powdery mold), in cereals, Erysiphe cichoracearum and Sphaerotheca fuliginea in cucurbits, Podosphaera leucotricha in apples, Uncinula neca tor in vines, Puccinia species in cereals, Rhizoctonia species .i, a¿ - ^ - jit-i .._ »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 Cinérea (gray mold) in strawberries, ornamentals, vegetables and vines, Cercospora arachidicola in peanuts, Pseudocercosporella herpotrichoides in wheat, barley, Pyricularia oryzae in rice, Phytophthora infestans in potatoes and tomatoes, Fusarium and Verticillium species in a variety of plants, Plasmopara vi Tícola in vines, Pseudoperonospora species in hops and cucumbers, Alternating species in vegetables and fruits and Mycosphaerella species in bananas.

In addition, the compounds I are suitable for controlling harmful fungi in the protection of materials (for example wood, paper, dispersions for paint, fibers or fabrics) and in the protection of ed products.

The compounds I are applied by treating the fungus or the plants, seeds, materials or soil that is to be protected against fungal infection with an active as fungal amount of the active ingredients. The application is made before or after the infection of the materials, plants or seeds by the fungus.

These become cuary formulations, such as solutions, emulsions, suspensions, powders, pastes and granules. The form of use depends on the purpose; in any case, the fine and uniform distribution of the compound according to the invention must be ensured. The formulations are prepared in a known manner, for example, by spreading the active ingredient with solvents and / or carriers, if desired using emulsifiers and dispersants, it also being possible to use other organic solvents as auxiliary solvents if the diluent used is water. The auxiliaries are mainly: solvents such as aromatics (for example, xylene), chlorinated aromatics (chlorobenzenes) paraffins (petroleum fractions), alcohols (methanol, butanol), ketones (cyclohexanone), amines (for example, ethanolamine, dimethylformamide) and water; carriers as crushed natural minerals (eg kaolins, clays, talc, chalk) and crushed synthetic materials (eg highly disperse silica, silicates; emulsifiers as nonionic and anionic emulsifiers (eg ethers of polyoxyethylene fatty alcohols, alkylsulfonates and arylsulfonates ) and dispersants as residual liquors of lignosulfite and methylcellulose.

In general, the fungicidal compositions comprise from 0.1 to 95% by weight, preferably from 0.5 to 90% by weight of the active ingredient.

Depending on the nature of the desired effect, the application rates are from 0.01 to 2.0 kg of the active ingredient per hectare when used in the protection of crops.

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

When used in the protection of ed 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, the normal application rates in the protection of materials are from 0.001 g to 2 kg, preferably 0.005 g to 1 kg, of the active ingredient per cubic meter of the treated material.

In their use as fungicides, the compositions according to the invention can also be - «_ &, _, __ * _. be present together with other active ingredients, for example with herbicides, insecticides, growth regulators, fungicides or even with fertilizers.

Mixing with fungicides often results in a broader spectrum of fungicidal action.

The following list of fungicides together with which the compounds according to the invention can be used is proposed to illustrate the possible combinations, but not to impose any limitations.

Sulfur, dithiocarbamates and their derivatives, such as iron (III) dimethyldithiocarbamate, zinc dimethyldithiocarbamate, zinc ethylenebisdithiocarbamate, manganese ethylenebisdithiocarbamate, manganese zinc ethylene diaminebisdithiocarbamate, tetramethylthiuram disulfide, ammonia complex of [N, N-ethylenebisdithiocarbamate] zinc, ammonia complex of zinc [N, N-propylenebisdithiocarbamate], zinc [N, N-propylenebisdithiocarbamate], N, N'-polypropylenebis (thiocarbamoyl) disulfide; nitro derivatives, such as dinitro (1-methylheptyl) phenylcrotonate, 2-sec-butyl-4,6-dinitrophenyl __ «é > _a - ** «« .-, »_ ^, ._", l____, 3, 3-dimethylacrylate, 2-sec-butyl-4,6-dinitrophenylisopropyl carbonate, diisopropyl 5-nitroisophthalate; heterocyclic substances as it may be 2-heptadecyl-2-imidazoline acetate, 2, 4-dichloro-6- (o-cloroanilmo) -s-triazine, 0,0-diethyl ftamilidofosfonotioato, 5-amino-l- [bis (dimethylamino) phosphinyl] 3-phenyl-1,2,4-triazole, 2,3-dicyano-1,4-dithioanthraquinone, 2-thio-l, 3-dithiolo [4,5-b] quinoxaline, methyl 1- (butylcarbamoyl) -2-benzimidazolecarbamate, 2-metoxicarbonilamidobencimidazol, 2- (2-furyl) benzimidazole, 2- (4-thiazolyl) benzimidazole, N- (1, 1, 2, 2-tetracloroetilt? o) tetrahidoftalimida, N-trichloromethylthiotetrahydrophthalimide, N- tpcloromethylthiophthalimide, N-dichlorofluoromethylthio-N1, N '-dimethyl-N-phenylsulfamide, 5-ethoxy-3-trichloromethyl-l, 2, 3-thiadiazole, 2-thiocyanatomethylthiobenzothiazole, 1-dichloro-2, 5-dimethoxybenzene, 4- (2 -chlorophenylhydrazono) -3-methyl-5-isoxazolone, pyridin-2-thiol 1-oxide, 8-hydroxyquinoline or its copper salt, 2,3-dihydro-5-carboxanilido-6-methyl-1, -oxatiin, 2 , 3-dihydro-5-carboxanilido-6-methyl-l, 4-oxathiane 4,4-dioxide, 2-methyl-5,6-dihydro-4H-pyran-3-carboxanilide, 2- ü- jAj-A'-it | _j -! _ fa_. ___ .. t,? J- «t ..» j ._ - -_,. ^ 'n-A _...... «A ...» .... ^ ..- t._ .. "- fl .. A -" - fcnl_ methylfuran-3-carboxanilide, 2, 5-dimethylfuran-3- carboxanilide, 2, 4, 5-trimetilfuran-3-carboxanilide, N-cyclohexyl-2, 5-dimethylfuran -3-carboxamide, N-cyclohexyl-N-methoxy-2, 5-dimethylfuran-3-carboxamide, 2- methylbenzanilide, 2-yodobenzanilida, N-formyl-N-morpholine 2, 2, 2-trichloroethyl acetal, piperazin-1 , 4-diylbis-1- (2,2, 2-trichloroethyl) formamide, 1- (3, -dichloroanilino) -1- formylamino-2,2,2-trichloroethane, 2,6-dimethyl-N-tridecylmorpholine or its salts, 2,6-dimethyl-N-cyclododecylmorpholine or its salts, N- [3- (p-tert-butylphenyl) -2-methylpropyl] -cis-2,6-dimethylmorpholine, N- [3- (p-ter -butylphenyl) -2-methylpropyl] piperidine, 1- [2- (2, 4-dichlorophenyl) -4-et? ll, 3-dioxolan-2-ylethyl] -1H- 1,2,4-triazole, 1- [2- (2,4-dichlorophenyl) -4-n-propyl-l, 3-dioxolan-2-ylethyl] -lH-1, 2,4-triazole, N- (n-propyl) -N- (2 , 4,6-trichlorophenoxyethyl) -N'-imidazolyl urea, 1- (4-chlorophenoxy) -3,3-dimethyl-1- (1 H-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) oxiran-2-ylmethyl] -lH-1, 2,4-triazole, a- (2 chlorophenyl) -a- (4-chlorophenyl) -5-pyrimidinemethanol, 5-butyl-2-dimethylamino-4-hydroxy-β-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-methoxyimino- [a- (o-tolyloxy) -tolyl] methyl acetate, E-2-. { 2- [6- (2-Cyanophenoxy) pyrimidin-4-yloxy] phenyl} -3-methoxyacrylate, N-methyl-E-methoximino- [a- (2-phenoxyphenyl)] acetamide, N-methyl-E-methoximino- [a- (2,5-dimethylphenoxy) -o-tolyl] acetamide , anilinopyrimidines such as N- (4,6-dimethylpyrimidin-2-yl) aniline, N- (4-methyl-1-6- (1-propynyl) pyrimidin-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, cinnamamides such as 3- (4-chlorophenyl) -3- (3,4-dimethoxyphenyl) acploylmorpholine, and a variety of fungicides, such as dodecylguanidine acetate, 3- [3- (3, 5-dimethyl-2-oxycyclohexyl) -2-hydroxyethyl] glutarimide, hexachlorobenzene, N- (2,6-dimethylphenyl) -N - (2-furoyl) -DL-alaninate methyl, DL-N- (2,6-dimethylphenyl) -N- (2'-methoxyacetyl) alanine methyl ester, N- (2,6-dimethylphenyl) -N-chloroacetyl -D, L-2- . ^. - _ ^ _-__ «__..._«.

Aminobutyrolactone, DL-N- (2,6-dimethylphenyl) -N- (phenylacetyl) alanine methyl ester, 5-methyl-5-vinyl-3- (3,5-dichlorophenyl) -2,4-dioxo-l, 3 -oxazolidine, 3- (3,5-dichlorophenyl) -5-methyl-5-methox? methyl-l, 3-oxazolidin-2,4-dione, 3- (3,5-dichlorophenyl) -1-isopropylcarbamoylhydantoin, N - (3,5-dichlorophenyl) -1,2-dimethylcyclopropan-1, 2-dicarboximide, 2-cyano- [N- (ethylaminocarbonyl) -2-methoximino] acetamide, 1- [2- (2,4-dichlorophenyl) pentyl] -1H-1,2, -triazole, 2,4-difluoro-a- (1H-1,2,4-triazolyl-1-methyl) benzhydryl alcohol, N- (3-chloro-2, 6-dinitro) -4- trifluoromethylphenyl) -5-tr? Fluoromethyl-3-chloro-2-aminopyridine, 1- ((bis (4-fluorophenyl) methyl-silyl) methyl) -1H-1,2,4-tr? Azole.

The active ingredients can be applied as formulations or it is possible to use the forms prepared therefrom, for example, in the form of directly sprayable solutions, powders, suspensions, or dispersions, emulsions, oily dispersions, pastes, powders, materials for dispersion. , or granules, by means of aspersion, atomization, dusting, dispersion or irrigation. The forms of use completely depend on the purpose, in any case, they must guarantee the finest possible distribution of the active ingredients | -_-___- > ffl _ *? _.- according to the invention.

The concentrations of the active ingredient in ready-to-use preparations can vary within 5 broad ranges.

In general, these are from 0.0001 to 10%, preferably from 0.01 to 1%.

The active ingredients can also be used with very good results in the ultra low volume method (VUL), it being possible to apply the formulations with about 95% by weight of the active ingredient or even the active ingredient without additives. The rate of application of the active ingredient to control pests is from 0.1 to 2.0, preferably from 0.2 to 1.0 kg / ha under field conditions. 20 Substances which are suitable for the preparation of directly sprayable solutions, emulsions, pastes or oily dispersions are fractions of mineral oil from medium to high boiling point, such as kerosene or diesel oil, in addition 25 tars and oils of vegetable and animal origin, aliphatic, cyclic 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, solvents strongly polar, for example, dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone or water.

Aqueous use forms can be prepared from emulsion concentrates, pastes or wettable powders (spray powders, oil dispersions) by adding water. To prepare emulsions, pastes or oily dispersions, the substances as such or dissolved in an oil or solvent, can be homogenized in water by means of wetting agent, thickener, dispersant or emulsifier. However, it is also possible to prepare concentrates composed of the active ingredient, the wetting agent, thickener, dispersant or emulsifier and, if desired, solvent or oil, and these concentrates are suitable for dilution with water.

Suitable surfactants are alkali metal salts, alkaline earth metal salts and ammonium salts of lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibultilnaphthalenesulfonic acid; alkylarylsulfonates, alkyl sulphates, alkyl sulphonates, fatty alcohol sulfates and fatty acids and their alkali metal and alkaline earth metal salts, sulphated fatty alcohol ether glycol ether salts, sulfonated naphthalene condensates and naphthalene derivatives with formaldehyde, naphthalene condensates or Naphthalenesulfonic acid with phenol and formaldehyde, polyoxyethylene octylphenyl ether, isooctylphenol ethoxylate, 10 octylphenol, nonylphenol, alkylphenyl polyglycol ethers, tributylphenyl polyglycol ether, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol / ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ether, ethoxylated polyoxypropylene, 15 lauryl alcohol polyglycol ether acetal, sorbitol esters, residual liquors of lignosulfite and methylcellulose.

The powders, dispersion materials and powders can be prepared by mixing or grinding the active ingredients with a solid carrier at the same time.

In general, the formulations comprise from 0.01 to 95% by weight, preferably from 0.1 to 90% by weight of the active ingredient. The active ingredients are 25 used in a purity from 90 to 100%, preferably Jí & and «28 95% up to 100% (according to the NMR spectrum) Examples of formulations are: I. 5 parts by weight of a compound according to the invention are intimately mixed with 95 parts by weight of finely divided kaolin. This produces a powder containing 5% by weight of the active ingredient.

II 30 parts by weight of a compound according to the invention are intimately mixed with a mixture of 92 parts by weight of pulverulent silica gel and 8 parts by weight of paraffin oil which has been dispersed on the surface of this silica gel . This provides a formulation of the active ingredient with good adhesive properties (content of the active ingredient 23% by weight).

III 10 parts by weight of a compound according to the invention are dissolved in a mixture composed of 90 parts by weight of xylene, 6 parts by weight of the addition product of 8 A 29 10 moles of ethylene oxide and 1 mole of N-monoethanolamide of oleic acid, 2 parts by weight of calcium dodecylbenzenesulfonate and 2 parts by weight of the addition product of 40 moles of ethylene oxide and 1 mole of castor oil (content of the active ingredient 9% by weight).

IV. 20 parts by weight of a compound according to the invention dissolve a mixture composed of 60 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 5 parts by weight of the addition product of 7 moles of ethylene oxide and 1 mol of isooctylphenol and 5 parts by weight of the addition product of 40 moles of ethylene oxide and 1 mole of castor oil (content of the active ingredient 16% by weight).

V. 80 parts by weight of a compound according to the invention are mixed thoroughly with 3 parts by weight of sodium diisobutyl naphthalene-sulfonate, 10 parts by weight of the sodium salt of a lignosulfonic acid from a residual liquor of sulfite and 7 parts by weight f l- t-? ¡__-___. - *, _--] _! , .-- * • »30 of pulverulent silica gel, and the mixture is ground in a hammer mill (content of the active ingredient 80% by weight).

SAW. 90 parts by weight of a compound according to the invention are mixed with 10 parts by weight of N-methyl-α-pyrrolidone; this produces a convenient solution for use in the form of microdroplets (content of the active ingredient 90% by weight).

VII 20 parts by weight of a compound according to the 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 addition product of 7 moles of ethylene oxide and 1 mole of isooctylphenol and 10 parts by weight of the addition product of 40 moles of ethylene oxide and 1 mole of castor oil. When the solution is emptied into 100,000 parts by weight of water and distributed therein an aqueous dispersion containing 0.02% by weight of the active ingredient is obtained.

VIII. 20 parts by weight of a compound according to the invention are mixed thoroughly with 3 parts by weight of sodium diisobutylnaphthalene-sulfonate, 17 parts by weight of the sodium salt of a lignosulfonic acid from the residual sulphite liquors and 60 parts by weight of pulverulent silica gel, and the mixture is ground in a hammer mill. The fine distribution of the mixture in 20,000 parts by weight of water produces a spray mixture containing 0.1% by weight of the active ingredient.

Granules, for example, coated granules, impregnated granules and homogeneous granules can be prepared by agglutinating the active ingredients to the solid carriers. Examples of solid carriers are mineral earths such as silica gel, silicas, silicates, talc, kaolin, clays, limestone, lime, chalk, bole, loes, clays, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate , magnesium oxide, crushed synthetic materials, fertilizers, for example ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and products of vegetable origin such as cereal flour, flour Ítt ¿4 ^? Áüa _- ^. ^ -_______________-, tree bark, wood flour and flour from walnut shells, cellulose powders and other solid carriers.

Different types of oils, or herbicides, fungicides or other pesticides or bactericides can be added to the active ingredients, if appropriate, also only just before use (in the tank mix). These agents can be mixed with the compositions according to the invention in a weight ratio from 1:10 to 10: 1.

Example 1 Methyl 2-cyano-3-methylbut-2-enotate 500 g (8.62 mol) of acetone were initially charged in 500 mL of benzene. 755 g (7.63 moles) of methyl cyanoacetate, 321 g (5.36 moles) of acetic acid and 57.7 g (0.75 moles) of ammonium acetate were mixed and the mixture was then refluxed for 10 hours, using a Dean-separator. Stark For the treatment, the reaction solution was washed twice with water and the organic phase was then dried over sodium sulfate and concentrated. This produced 691 g of the crude product from which 2-cyano-3-methylbut-2- was isolated methyl ethoxylate as a colorless liquid by distillation (226 g, yield 57%). 1H-NMR (CDC13, in ppm): 2.3; 2.4; 3.8.

Example 2 Methyl l-cyano-2, 2, 3, 3-tetramethyl-l-cyclopropanecarboxylate 5. 6 g (50 mmol) of potassium tert-butoxide were initially charged in 15 mL of DMSO. Then 4.4 g (50 mmol) of 2-nitropropane were dissolved in 190 mL of DMSO, and the mixture was slowly added dropwise. Finally, 5 g (36 mmol) of methyl 2-cyano-3-methylbut-2-enoate previously synthesized, dissolved in 10 mL of DMSO, were added dropwise and the mixture was stirred overnight. For the treatment, the reaction was quenched with water and the mixture was then extracted three times with methyl tert-butyl ether. The organic phase was washed twice with water, then dried using sodium sulfate and finally concentrated in a rotary evaporator. This yielded 4.7 g of purely pure methyl l-cyano-2, 2,3,3-tetramethylcyclopropanecarboxylate as a product (yield 72%). 1 H-NMR (CDCl 3, ppm): 1.4; 3.75. '^, v and 34 Example 3 L-cyano-2, 2,3, 3-tetramethylcyclopropanecarboxylic acid 5 135 g of methyl l-cyano-2, 2, 3, 3-tetramethylcyclopropanecarboxylic acid (0.75 mol) in a mixture of 1.05 L each of methanol, tetrahydrofuran and 2 N aqueous sodium hydroxide solution were refluxed for 6 hours. hours. After cooling, the mixture was acidified with a concentrated sulfuric acid [sic] and extracted three times with methylene chloride. The extract was dried with sodium sulfate and the solvent was removed in a rotary evaporator, and the product was then isolated in 15 high purity (103.9 g, 83% yield). 1H-NMR (CDC13, in ppm): 1.4; 9.9.

Example 4 20 (IR) -N- (4-n-trophenyl) et? L-l-cyano-2, 2, 3, 3-tetramethylcyclopropanecarboxamide 4. 95 g (29.6 mmol) of l-cyano-2,2,3,3-tetramethylcyclopropanecarboxylic acid were initially 25 charged in 100 mL of methylene chloride. They were added 35, « 5. 99 g of triethylamine (59.3 mmol), 6 g of (lR) -4-nitrophenethylamine (29.6 mmol) and 4.67 g of diethyl cyanophosphonate (29.63 mmol) and the mixture was then stirred overnight at room temperature. Without aqueous treatment, the reaction mixture was directly subjected to column chromatography using methyl terbutyl ether as the mobile phase. It was possible to isolate 7.1 g of the product (IR) -N- (4-nitrophenyl) ethyl-1-cyano, 2, 2, 3, 3-tetramethylcyclopropanecarboxamide as a white solid (yield 76%). 1 H-NMR (CDC13, in ppm): 1.3; 1.4; 1.55; 6.6; 7.5; 8.2.

Example 5 (IR) -N- (2,4-dichlorophenyl) ethyl-l-cyano-2,2,3,3-tetramethylcyclopropanecarboxamide 1. 0 g (6 mmol) of l-cyano-2,2,3,3-tetramethylcyclopropanecarboxylic acid were initially charged in 20 mL of methylene chloride. 1.21 g of triethylamine (12 mmol) 1.14 g of (IR) -2,4-dichlorophenethylamine (6 mmol) and 0.98 g of diethyl cyanophosphonate (6 mmol) were added, and the mixture was then stirred at room temperature overnight. With no other aqueous treatment, the reaction mixture was subjected to 36 directly to column chromatography using methyl terbutyl ether as the mobile phase. It was possible to isolate 2.0 g of the product (IR) - (2, 4-dichlorophen? L) et? L-1-c? An- 2, 2, 3, 3-tetramethylc? Clopropancarboxamide as a white solid (yield 98% ). 1 H-NMR (CDC13, in ppm): 1.25; 1.35; 1.5; 5.3; 6.8; 7.25.

Example 6 10 Fungicidal action The fungicidal action of the compounds of the formula I against harmful fungi was demonstrated by the following greenhouse experiments. 15 a) The active ingredients were formulated as a 20% strength emulsion in a mixture of 70% by weight of cyclohexanone, 20% by weight of Nekanil® LN (Lutensol® AP6, wetting agent that 20 has an emulsifying and dispersing action, based on ethoxylated alkylphenols) and 10% by weight of Emulphor® EL (Emulan® EL, emulsifier based on ethoxylated fatty alcohols) and diluted with water to obtain the desired concentration. 25 ______ft_____ ___________ b) Activity against Pyricularia oryzae (protective) Leaves of rice seedlings "Tai-Nong 67" grown in pots were sprayed to the point of drip with an aqueous preparation of the active ingredient that had been prepared from a standard solution of 10% active ingredient, 63% cyclohexanone and 27% of the emulsifier. The next day, the plants were inoculated with an aqueous spore suspension of Pyricularia oryzae. The test plants were then placed in conditioned chambers at a temperature of 22-24 ° C and 95-99% relative atmospheric humidity for 6 days. The degree of infection development in the leaves was then determined visually.

A = Compound of JP 89-55786.

B B = compound of example 5 Results What was measured was the percentage infection of the leaves after the application of a preparation of the s ^ A ^ j ^ l _a_ «fttr-'affifcf active ingredient containing 16 ppm. The untreated plants were infected up to 70%. This value was used as a reference (100%). The plants that were treated with the active ingredient A still showed 50% fungal infection, while the plants treated with the active ingredients B and C according to the invention showed no fungal infection or a fungal infection of only 5%.

Claims (3)

1. A cyclopropanecarboxamide of the formula I where : Ri is Ci-Cg alkyl or C2-Cg alkenyl, where these radicals can be partially or completely halogenated and / or can carry one or two of the following groups: C, L-C4 alkoxy, C?-C haloalkoxy, C? -C alkylthio, C1-C4 alkoxycarbonyl, C3-C6 cycloalkyl, and phenyl, wherein the phenyl ring may be partially or completely halogenated and / or may carry from one to three of the following radicals: nitro, cyano, C 1 -C 4 alkyl, C 1 -4 haloalkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 alkylthio, C 3 -C 6 cycloalkyl or heterocyclyl R 'is hydrogen or has one of the meanings of the radical R independently of the meaning of R R "is hydrogen or Ci-Cß alkyl; And it is cyano or halogen; W is phenyl, where this radical can carry from one to three of the following groups: nitro, halogen, cyano, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, alkylthio of C1-C4, C3-C6 cycloalkyl and C1-C4 alkoxycarbonyl in the form of the R-enantiomer and its salts useful in agriculture, except for the compound N- [1- (4-chlorophenyl) ethyl] -1-cyano-2,2,3,3-tetramethylcyclopropanecarboxamide in racemic form.

The cyclopropanecarboxamide of formula I as recited (e.n claim 1, wherein R is C? -C6 alkyl.

3. The cyclopropanecarboxamide of formula I as claimed in claim 1 or 2, wherein R is _ < ._ .IÜ ??? L hydrogen, The cyclopropanecarboxamide of the formula I as claimed in any of claims 1 to 3, 3 wherein R is hydrogen. The cyclopropanecarboxamide of formula I as claimed in any of claims 1 to 4, wherein Y is cyano. The cyclopropanecarboxamide of the formula I as claimed in any of claims 1 to 5, wherein W is at least mono- or disubstituted by nitro, halogen, Ci-Cs alkyl, Ci-Cg haloalkyl, Ci-haloalkoxy, Cg or C? -C6 alkoxy? The cyclopropanecarboxamide as claimed in claim 6, wherein W is a phenyl group that is disubstituted, the substituents being located at the 2 and 4 position of the phenyl ring. The cyclopropanecarboxamide as claimed in any of claims 6 or 7, wherein the substituent at the 2-position is selected from the group consisting of halogen, methyl, methoxy and ___ Wii ___._ l .___ - ..... _ r '»Éiíi- i J _-_ ,, .....» __, j «.- a - .... > A _-_ J__, * ..___-_-_, _ cyano. The cyclopropanecarboxamide as claimed in any of claims 6 to 8, wherein the substituent at the 4-position is selected from the group consisting of halogen, methyl, methoxy, fluorine and cyano. The cyclopropanecarboxamide as claimed in any of claims 6 to 9, wherein the phenyl ring is 2,4-dichlorophenyl. The cyclopropanecarboxamide as claimed in any of claims 1 to 10, wherein the cyclopropyl ring is l-cyano-2, 2,3, 3-tetramethylcyclopropane. A composition containing an amount that is effective to control deleterious fungi of at least one cyclopropanecarboxamide of formula I as claimed in any of claims 1 to 11 and at least one inert liquid and / or solid carrier and, if appropriate, at least one surfactant and, if appropriate, an active ingredient, such as an insecticide. A method for controlling harmful fungi, which consists of treating the harmful fungi, their habitat or the plants, areas, materials or spaces that have to be kept free of them with an effective amount of a cyclopropanecarboxamide of the formula I as claimed in any of claims 1 to 11. The use of a cyclopropanecarboxamide of the formula I as claimed in any of claims 1 to 11 as an active ingredient for controlling harmful fungi, the active ingredient having reduced phytotoxicity. The use of a cyclopropancarboxamide of the formula I as claimed in any of claims 1 to 11 as an active ingredient for preparing compositions for the protection of crops having fungal action, the composition for the protection of crops being suitable for application in the boxes of the seedlings, because the active ingredient has systemic action and is taken or taken up by the roots. SUMMARY OF THE INVENTION The cyclopropancarboxamides of the formula I are described: where: RJ is Ci-Cß alkyl or C2-Cg alkenyl, where these radicals can be partially or completely halogenated and / or can carry one or two of the following groups: C1-C4 alkoxy, C1-C4 haloalkoxy, C1 alkylthio -C4, C? -C alkoxycarbonyl, C3-C6 cycloalkyl, and phenyl, wherein the phenyl ring may be partially or completely halogenated and / or may carry from one to three of the following radicals: nitro, cyano, C1-alkyl -C4, C1-C4 haloalkyl, C] _-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio, C3-C6 cycloalkyl or heterocyclyl R 'is hydrogen or has one of the meanings of the radical R,? regardless of the meaning of R R "is hydrogen or C? -Cg alkyl; is cyano or halogen; w is phenyl, wherein this radical can carry from one to three of the following groups: nitro, halogen, cyano, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C? -C4 alkylthio, C3-C6 cycloalkyl and C? -C4 alkoxycarbonyl and its forms with optical activity and the salts useful in agriculture, except for the compound N- [1- (4-chlorophenyl) ethyl] -1- cyano-2,2,3,3-tetramethylcyclopropanecarboxamide in racemic form. DIF t?