MXPA00002529A - Benzamidoxim derivatives, intermediate products and methods for preparing and using them as fungicides - Google Patents

Abstract

The invention relates to benzamidoxim derivatives of formula (I) wherein the substituents have the following meanings:R1 represents difluoromethyl or trifluoromethyl, R2 represents hydrogen or fluorine, R3 represents C1-C4 alkyl optionally substituted with cyano, C1-C4 halogenalkyl, C1-C4 alkoxy- C1-C4 alkyl, C3-C6 alkenyl, C3-C6 halogenalkenyl, C3-C6 alkinyl, C3-C8 cycloalkyl- C1-C4 alkyl, R4 represents phenyl- C1-C6 alkyl, which can carry one or more substituents selected from the group composed of halogen, C1-C4 alkyl, C1-C4 halogenalkyl, C1-C4 alkoxy or C1-C4 halogenalkoxy on the phenyl ring, or thienyl- C1-C4 alkyl, which can carry one or more substituents selected from the group composed of halogen, C1-C4 alkyl, C1-C4 halogenalkyl, C1-C4 alkoxy or C1-C4 halogenalkoxy on the thienyl ring, or pyrazol- C1-C4 alkyl, which can carry one or more substituents selected from the group composed of halogen, C1-C4 alkyl, C1-C4 halogenalkyl, C1-C4 alkoxy or C1-C4 halogenalkoxy on the pyrazol ring. The invention also relates to intermediate products for the preparation of these derivatives and to their use as fungicides.

Description

NEW BENZAMIDOXIMA DERIVATIVES, INTERMEDIARIES AND PROCESSES FOR PREPARATION AND USE AS FUNGICIDES The present invention relates to novel benzamidoxime derivatives, processes and intermediates for their preparation and their use as fungicides. JP-A 02/006453 describes active benzamidoxime derivatives as fungicides which, however, are not completely satisfactory, in particular when low application rates are used. It is an object of the present invention to offer novel benzamidoxime derivatives that have better activity, in particular at even low application rates. We have found that this goal is achieved by the benzamidoxime derivatives of the formula I where R is difluoromethyl or trifluoromethyl, 2 R is hydrogen or fluorine R is C 1 -C 4 alkyl which may be substituted by cyano, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy C 1 -C 4 alkyl, C 3 alkenyl -C6, C3-C6 haloalkenyl, C3-C6 alkynyl, C3-C8 cycloalkyl-C1- C4 alkyl, R is phenylalkyl of Oj-Cß which can carry one or more substituents selected from the group consisting of halogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy and C 1 -C 4 haloalkoxy on the phenyl ring, or is C 1 -C 4 alkyl thienyl which may carry one or more substituents selected from the group consisting of halogen, C 1 -C 4 alkyl / C 2 -C 4 haloalkyl, C 1 -C 4 alkoxy and C 1 -C 4 haloalkoxy in the thienyl ring, or is pyrazolyl C 1 -C 4 alkyl which can carry one or more substituents selected from the group consisting of halogen, C 3 -C 4 alkyl, C 3 -C 4 haloalkyl, C 1 -C 4 alkoxy and C 1 -C haloalkoxy in the pyrazole ring. In the definition of substituents, R 1 to R 4, the terms indicated are a collective term for a group of compounds. Halogen in each case is fluorine, bromine, chlorine or iodine, in particular fluorine or chlorine. Other meanings are, for example: - C 1 -C alkyl: methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl or 1,1-dimethylethyl, in particular ethyl; C1-C4 haloalkyl: an alkyl radical of C3.-C4, as already mentioned, which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, for example trichloromethyl, trifluoromethyl, 2-fluoroethyl, 2-chloroethyl , 2-bromoethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2,2,2-trichloroethyl, 2-fluoropropyl, 3-fluoropropyl, 2-chloropropyl or 3-chloropropyl, in particular 2-fluoroethyl or chloroethyl; C1-C4 cyanoalkyl: for example cyanomethyl, 1-cyanoet-1-yl, 2-cyanoethyl-1-yl, 1-cyanoprop-1-yl, 2-cyanoprop-1-yl, 3-cyanopropyl-1-yl, l-cyanoprop-2-yl or 2-cyanoprop-2-yl, in particular cyanomethyl or 2-cyanoethyl; C1-C4 alkoxy; methoxy, ethoxy, n-propoxy, 1-methylethoxy, n-butoxy, 1-methylpropoxy, 2-methylpropoxy or 1,1-dimethylethoxy, in particular methoxy or ethoxy; C.sub.1 -C.sub.4 alkoxy C.sub.1 -C.sub.12 alkyl C.sub.1 -C.sub.4 alkyl which may be substituted C.sub.1 -C.sub.1 alkoxy as already mentioned, ie, for example, methoxymethyl, ethoxymethyl, n-propoxymethyl, methylethoxy) methyl, n-butoxymethyl, (1-methylpropoxy) ethyl, (2-ethylpropoxy) ethyl, (1,1-dimethylethoxy) ethyl, 2- (methoxy) ethyl or 2- (ethoxy) ethyl, in particular methoxymethyl or -methoxyethyl; C3-C5 alkenyl: for example prop-2-en-l-yl, n-buten-4-yl, l-methylprop-2-en-l-yl, 2-methylprop-2-en-1-yl or 2-buten-1-yl, in particular prop-2-en-1-yl; C3-C6 haloalkenyl: C3-C6 alkenyl as already mentioned is partially or completely substituted by fluorine, chlorine and / or bromine, for example 2- * chloroalyl, 3-chloroallyl, 2,3-dichloroalyl or 3, 3 -dichloroalyl, in particular 2-chloroalyl; C3-C6 alkynyl for example prop-1-yn-l-yl, prop-2-yn-l-yl, n-but-1-yn-l-yl, n-but-l-yn-3-yl , n-but-1-in-4-yl or n-but-2-yn-l-yl, in particular prop-2-yn-l-yl; C3-Cβ cycloalkyl-C1-C4 alkyl for example cyclopropyl ethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, (cyclopropyl) ethyl, 1- (cyclobutyl) ethyl, 1- (cyclopentyl) ethyl, 1- (cyclohexyl) ethyl, 1- (cycloheptyl) ethyl, 1- (cyclooctyl) ethyl, 2- (cyclopropyl) ethyl or 2- (cyclobutyl) ethyl, in particular cyclopentylmethyl; Ci-Ce phenylalkyl: for example benzyl, 1-phenylethyl, 2-phenylethyl, 1-phenylprop-1-yl, 2-phenylprop-1-yl, 3-phenylprop-1-yl, in particular benzyl or 2-phenylethyl; thienylalkyl of C 1 -C 4: for example 2-thienylmethyl, 3-thienylmethyl or 2-thienylethyl; C 1 -C 4 -cycloalkyl: for example 1-pyrazolylmethyl, 2-pyrazolylmethyl, 3-pyrazolylmethyl or 2-pyrazolyl-ethylthio [sicj.

The compounds in which the R substituent is 3-difluoromethyl, the substituent R is cyclopropylmethyl and the substituent R is benzyl which [lacuna] one to three substituents selected from the aforementioned group on the phenyl ring, in particular one to three selected substituents of the group consisting of fluorine, chlorine, methyl, methoxy and trifluoromethyl have generally proved to be especially effective. The compounds of the formula I, wherein R to R have the meanings mentioned in the following Table 1 are particularly preferred.

Table 1 In the previous table, cPr is cyclopropylmethyl In the above table, cPr is cyclopropylmethyl [sic] The benzamidoxime derivatives according to the invention of the formula I are obtained by the process according to the invention by means of an ether dissociation of benzonitriles fluorinated of the formula II, the reaction of the resulting benzonitriles III with haloalkanes CHffiFnHal (m has the value of 0 or 1, n the value of 2 or 3), such as CHF2CI or CF3I, in an alkaline medium (preferably in presence of an alkali metal hydroxide) to obtain the IV benzonitriles and the subsequent reaction of IV with hydroxyl ina or salts thereof in aqueous solution, preferably in water or water / alkanol mixtures, in the presence or absence of a base, for obtain the benzamidoximes of the formula V, which are subsequently alkylated in a manner known per se to obtain the VI precursors. The benzamidoximes VI can then be acylated in a manner known per se with suitable acyl halides, preferably suitable acyl chlorides, by heating in inert solvents (preferably from 20-100 ° C). Particularly suitable inert solvents are hydrocarbons or ethers, especially preferably aromatic hydrocarbons such as toluene or xylene, to mention only two examples.

? V R in the above equation is a CHmFn group, where it is 0 or l and n is 2 or 3. The intermediaries of formula III, where R2 [sicj is fluorine and the intermediates of formulas IV, V and VI, all of which are In the above equation, they are novel and also form part of the object of the invention. Started from 2, 3-difluoro-6-methoxybenzaldehyde (which can be prepared, for example, by the process of Example 27 of WO 97/03071), the preparation of these novel Intermediates having a difluoro substitution can be carried out through the step of the IV compounds using the variants described in Example 2.

The other steps in the preparation of the corresponding compounds V and VI are known per se by those skilled in the art. The preferred compounds of formulas IV, V and VI are those wherein R 2 and R 3 (compounds VI) have the meanings given in the above for the compounds of the formula I. Preferred compounds of formula IV are the compounds provided in the following Table 2 (m and n have the meanings mentioned above).

The preferred substrates of formula V are given in Table 3 Some preferred cofactors of formula VI are given in Table 4 below.

Compounds I are distinguished by outstanding activity against a broad spectrum of phytopathogenic fungi, in particular from the classes of ascomycetes, deuteromycetes, phycomycetes and basidiomycetes. Some of these act in a systemic way, and can, therefore, be used as fungicides with action in leaves and soils. Normally, the plants are sprayed or sprinkled with the active ingredients, or the seeds of the plants are treated with the active ingredients. 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 water is used as a diluent. The auxiliaries which are suitable are essentially: solvents such as aromatics (for example xylene), chlorinated aromatics (for example chlorobenzenes), paraffins (for example mineral oil fractions), alcohols (for example methanol, butanol), ketones (for example cyclohexanone) ), amines (for example ethanolamine, dimethylformamide) and water; carriers as crushed natural minerals (e.g. kaolins, clays, talc, chalk) and crushed synthetic minerals (e.g., highly dispersed silicas, silicates); emulsifiers as nonionic and anionic emulsifiers (for example ethers of polyoxyethylene fatty alcohols, alkylsulfonates and arylsulfonates) and dispersants as residual liquors of lignosulfite and methylcellulose. Suitable surfactants are the alkali metal salts, alkaline earth metal salts and ammonium salts of aromatic sulfonic acids, for example, ligno-, phenol-, naphthalene- and dibutylnaphthalenesulfonic acid, and of fatty acids, alkyl sulfonates, alkylarylsulfonates, alkyl sulfates , lauryl ether sulfates and sulfates of fatty alcohols, and salts of sulphonated hexa-, hepta- and octadecanols, and of glycol ethers of fatty alcohols, condensates of sulfonated naphthalene and their derivatives with formaldehyde, condensates of naphthalene or of naphthalenesulfonic acids with phenol or formaldehyde, polyoxyethylene octylphenol ether, ethoxylated iso-octylphenol, octylphenol or nonylphenol, alkylphenol [sicj polyglycol ether, tributylphenyl polyglycol ether, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol / ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers or polyoxypropylene, lauryl alcohol polyglycol ether acetate, sorbitol esters, liquor is residual of lignosulfite and methylcellulose. The powders, dispersion materials and powders can be prepared by mixing or concomitantly grinding the active substances with a solid carrier. The granules, for example, coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active ingredients to the solid carriers. The solid carriers are mineral earth, such as silica gel, silicas, silica gels [sil], silicates, talc, kaolin, limestone, quick lime, gypsum, calcareous ferruginous clay, loess, clay, dolomite, eas land, calcium sulfate, magnesium sulfate, magnesium oxide, crushed synthetic materials, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and products of plant origin such as cereal flour, tree bark meal, wood flour and nutmeat meal, cellulose powder or other solid carriers. The following are examples of such formulations: a solution, suitable for use in the form of microdroplets, of 90 parts by weight of a compound I according to the invention and 10 parts by weight of N-methyl-2-pyrrolidone; II, a mixture of 10 parts by weight of a compound I according to the invention, 70 parts by weight of xylene, 10 parts by weight of the addition product of 8 to 10 moles of ethylene oxide and 1 mole of oleic acid N - monoethanolamide, 5 parts by weight of calcium dodecylbenzenesulfonate, 5 parts by weight of the addition product of 40 moles of ethylene oxide and 1 mole of castor oil; a dispersion is obtained by finely distributing the solution in water. III. an aqueous dispersion of 10 parts by weight of a compound I according to the invention, 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the addition product of 40 moles of ethylene oxide and 1 mol of castor oil; IV. an aqueous dispersion of 10 parts by weight of a compound I according to the invention, 25 parts by weight of cyclohexanol, 55 parts by weight of a mineral oil, fraction of boiling point 210 to 280 ° C and 10 parts by weight of the addition product of 40 moles of ethylene oxide and 1 mole of castor oil; V. a mixture, crushed in a hammer mill, of 80 parts by weight, preferably of a solid compound I according to the invention, 3 parts by weight of sodium di-iso-butylnaphthalene-2-sulfonate, 10 parts by weight of the sodium salt of a lignosulfonic acid from a residual sulphite liquor and 7 parts by weight of pulverulent silica gel, a spray mixture is obtained by finely distributing the mixture in water; SAW . an intimate mixture of 3 parts by weight of a compound I according to the invention and 97 parts by weight of finely divided kaolin; this powder consists of 3% by weight of the active ingredient; VII. an intimate mixture of 3 parts by weight of a compound I according to the invention, 62 parts by weight of pulverulent silica gel and 8 parts by weight of paraffin oil which has been sprayed onto the surface of this silica gel; this formulation imparts good adhesion for the active ingredient; VIII. an aqueous, stable dispersion of 40 parts by weight of a compound I according to the invention, 10 parts by weight of the condensate sodium salt of a phenolsulfonic acid / urea / formaldehyde, 2 parts by weight of silica gel and 48 parts in weight of water; this dispersion can also be diluted; IX. an oily, stable dispersion of 20 parts by weight of a compound I according to the invention, 2 parts by weight of calcium dodecylbenzenesulfonate, 8 parts by weight of polyglycol ether fatty alcohol, 20 parts by weight of the condensate sodium salt of a phenolsulfonic acid / urea / formaldehyde and 50 parts by weight of a paraffin mineral oil.

The novel compounds are distinguished by an over-active activity against a broad spectrum of phytopathogenic fungi, in particular from the class of the deutero icetes, ascomycetes, phycomycetes and basidiomycetes. Some of these act in a systemic way, and can be used as fungicides of action in leaves and soils. These are especially important for controlling a large number of fungi on a variety of cultivated plants such as wheat, barley, rye, oats, rice, corn, turf, cotton, soy, coffee, sugar cane, grapes, fruit, ornamental and vegetable species as cucumbers, beans and cucurbits, and on the seeds of these plants. The compounds are applied by treating fungi, or seeds, plant material or soil that is to be protected against fungal infection, with an effective amount as a fungicide of the active ingredients. The application is carried out before or after the infection of the materials, plants or seeds by the fungi. Specifically, the novel compounds 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 necator in vines, Puccinia species in cereals, Rhizoctonia species in cotton and turf, Ustilago species in cereals and sugarcane, Venturia inaequalis (scab) in apples, Helminthosporium species in cereals, Septoria nodorum in wheat, Botrytis cinerea (gray mold) in strawberries, vines, ornamentals and vegetables, Cercospora arachidicola in peanuts, Pseudocercosporella herpotrichoides in wheat, barley, Pyricularia oryzae in rice, Phitophthora infestans in potatoes and tomatoes, Fusarium and Verticillium species in a variety of plants, Plasmopara viticulture on vines and Alternarla species in fruits and vegetables. The novel compounds can also be used in the protection of materials (wood protection), for example, against Paecilomyces variotii. In general, the fungicidal compositions contain from 0.1 to 95, preferably from 0.5 to 90% by weight of the active ingredient. Depending on the nature of the desired effect, the application amounts are from 0.025 to 2, preferably from 0.1 to 1 kg of the active ingredient per hectare. In the treatment of the seed, amounts of 0.001 to 50, preferably 0.01 to 10 g of the active ingredient are generally required per kg of seed. In the form of use as fungicides, the agents according to the invention may also be present together with other ingredients, for example, with herbicides, insecticides, growth regulators, fungicides or even with fertilizers.

Often a mixture with fungicide gives rise to a wider spectrum of action as a fungicide. The following list of fungicides together with which the compounds according to the invention can be applied is proposed to illustrate the possible combinations, but not to impose any limitations: Sulfur, dithiocarbates and their derivatives, such as iron dimethyl dithiocarbamate ( III), zinc dimethyldithiocarbamate, zinc ethylenebisdithiocarbate, manganese ethylene bisdithiocarbamate, manganese zinc ethendithiumcarbamate, tetramethylthiuram disulfides [sic], zinc (N, N-ethylenebisdithiocarbamate) ammonia complex, ammonia complex of (N / N-propylenebisdithiocarbamate) of zinc, ammonia complex of zinc (N, N-propylenebisdithiocarbamate), N, N'-polypropylenebis (thiocarbamaoyl) disulfide; nitro derivatives, such as dinitro- (1-methylheptyl) phenyl crotonate, 2-sec-butyl-4,6-dinitrophenyl 3,3-dimethylacrylate, 2-sec-butyl-4,6-dinitrophenylisopropyl carbonate, diisopropyl 5-nitro-isophthalate; heterocyclic substances, such as 2-heptadecyl-2-imidazoline acetate, 2,4-dichloro-6- (o-chloroanilino) -s-triazine, 0.0-diethyl phthalimidophosphothioate, 5-amino-l- [bis (dimethylamino) phosphinil ] -3-phenyl-1,2,4-triazole, 2,3-dicyano-1,4-dithioanthraquinone, 2-thio-l, 3-dithiolo [4,5-bjquinoxaline, methyl 1- (butylcarbamoyl) -2 -benzimidazolcarbamate, 2-methoxycarbonylaminobenzimidazole, 2- (2-furyl) benzimidazole, 2- (4-thiazolyl) benzimidazole, N- (1, 1,2,2-tetrachloroethylthio) tetrahydrophthalimide, N-trichloroethylthiotetrahydrophthalimide, N-trichloro Ethylthiophthalimide, N-dichlorofluoromethyltio-N ', N'-dimethyl-N-phenylsulfodiamide, 5-ethoxy-3-trichloromethyl-1,2,3-thiadiazole, 2-thiocyanatomethylthiobenzothiazole, 1,4-dichloro-2,5-dimethoxybenzene, 4- (2-chlorophenylhydrazono) -3-methyl-5-isoxazolone / pyridine-2-thione 1-oxide, 8-hydroxyquinoline or its copper salt, 2,3-dihydro-5-carboxanilido-β-methyl-l, 4- oxathiane, 2,3-dihydro-5-carboxanilido-β-methyl-1,4-oxathiane 4,4-dioxide, 2-methyl-5,6-dihydro-4H-pyran-3-carboxanilide, 2-methylfuran-3 -carboxanilide, 2,5-dimethyl-furan-3-carboxanilide, 2,4-trimethyl-furan-3-carboxanilide, N-cyclohexyl-2,5-dimethyl-furan-3-carboxamide, N-cyclohexyl-N-methoxy-2, 5 -dimethylfuran-3-carboxamide, 2-methylbenzanilide, 2-iodobenzanilide, N-formyl-N-morpholin-2, 2, 2-trichloroethyl acetal, piperazin-1,4-diylbis- (1- (2,2,2- trichloroethyl) formamide [sic], 1- (3,4-dichloroanilino) -1-formylamino-2,2,2-trichloroethane; 2, β-dimethyl-N-tridrylmorpholine or its salts, 2,6-dimethyl-N-cyclododecylmorpholine or its salts, N- [3- (p-tert-butylphenyl) -2-methylpropyl] -cis-2, 6- di ethylmorpholine, N- [3- (p-tert-butylphenyl) -2-methylpropyl] piperidine, 1- [2- (2,4-dichlorophenyl) -4-ethyl-l, 3-dioxolan-2-ylethyl ] -1H-1, 2,4-triazole, 1- [2- (2,4-dichlorophenyl) -4-n-propyl-1,3-dioxolan-2-yl-ethyl] -1H-1, 2, 4-triazole, N- (n-propyl) -N- (2,4,6-trichlorophenoxyethyl) -N'-imidazolyl urea, 1- (4-chlorophenoxy) -3,3-dimethyl-1- (1H-1) , 2,4-triazol-1-yl) -2-butanone, (2-chlorophenyl) - (4-chlorophenyl) -5-pyrimidine-methanol, 5-butyl-2-dimethylamino-4-hydroxy-6-methylpyrimidine, bis (p-chlorophenyl) -3-pyridinemethanol, 1,2-bis (3-ethoxycarbonyl-2-thioureido) benzene, 1,2-bis (3-methoxycarbonyl-2-thioureido) benzene, [2- (4-chlorophenyl) ) ethyl] - (1,1-dimethylethyl) -1H-1,2,4-triazole-1-ethanol, 1- [3- (2-chlorophenyl) -1- (4-fluorophenyl) oxirane-2-ylmethyl] -1H-1, 2,4-triazole, and a variety of fungicides, such as dodecylguanidine acetate, 3- [3- (3, 5-dimethyl-2-oxycyclohexyl) -2-hydroxyethylglutarimide, hexachlorobenzene, methyl N- (2,6-dimethylphenyl) -N- (2-furoyl) -DL-alaninate, DL-N- (2,6-dimethylphenyl) - N- (2'-methoxyacetyl) alanine methyl ester, N- (2,6-dimethylphenyl) -N-chloroacetyl-D, L-2-amino-butyrolactone, DL-N- (2,6-dimethylphenyl) -N- (phenylacetyl) lanin methyl ester, 5-methyl-5-vinyl-3- (3,5-dichlorophenyl) -2, -dioxo-l, 3-oxazolidine, 3- [(3,5-dichlorophenyl) -5-methyl) -5-methoxymethyl-1,3-oxazolidin-2,4-dione [sic], 3- (3,5-dichlorophenyl) -1-isopropylcarbamide hydantoin, N- (3,5-dichlorophenyl) -1, 2- dimethylcyclopropan-1, 2-dicarboxamide, 2-cyano- [N- (ethylaminocarbonyl) -2-methoximino] acetamide, 1- [2- (2,4-dichlorophenyl) pentyl] -1H-1,2,4-triazole, 2 , 4-difluoro-a- (1H-1, 2,4-triazolyl-l-methyl) benzhydryl alcohol, N- (3-chloro-2,6-dinitro-4-trifluoromethyl-phenyl) -5-trifluoromethyl-3-chloro -2-a inopyridine, 1- ((bis (4-fluorophenyl) methylsilyl (methyl) -1H-1, 2,4-triazole, strobilurins such as methyl E-methoximino- [a- (o-tolyloxy) -o-tolyl-acetate, E-2-. { 2- [6- (2-Cyanophenoxy) pyridimin-4-yloxy] phenyl} Methyl-3-methoxyacrylate, N-methyl-E-methoximino- [α- (2,5-dimethyloxy) -o-tolyl] acetamide.

Anilinopyrimidines such as N- (4,6-dimethylpyridimin-2-yl) aniline, N- [4-methyl-d- (l-propynyl) pyrimidin-2-yl] niline, N- [4-methyl-6-cyclopropylpyridimin- 2-yl] aniline. Phenylpyrroles such as 4- (2, 2-difluoro-1,3-benzodioxol-4-yl) pyrrole-3-carbonitrile. Cinnamides such as 3- (4-chlorophenyl) -3- (3,4-dimethoxy-phenyl) -cyloylmorpholine.

Example 1 a) 6-fluoro-2-hydroxybenzonitrile 7.8 g of 2-methoxy-6-fluorobenzonitrile and 18.0 g of pyridine hydrochloride were heated for 5 hours at 195 ° C under dry nitrogen. After cooling, the batch was separated between 50 ml of water and 50 ml of tert-butyl methyl ether, and the organic phase was subsequently extracted with 40 ml of 2N NaOH. The alkaline extract was taken to pH 5 and subsequently extracted twice with 40 ml in each case of tert-butyl methyl ether. After the solvent had been evaporated, 4.7 g of the desired product was obtained as an oil (HPLC: 93%). NMR (DMSO) ppm: 6.8-6.95 m (2H); 7.5-7.6 m (lH); 11.8 s, br (1H) b) 2-difluoromethoxy-6-fluorobenzonitrile 6.3 g of chlorodifluoromethane were passed to a stirred mixture of 10.0 g of 2-hydroxy-6-fluorobenzonitrile, 50 ml of 1,2-dimethoxyethane and 25 ml of NaOH (33%) a 75 ° C (the reflux condenser was cooled with dry ice), and the stirring was continued for 1 hour at 70-75 ° C. After cooling, the batch was diluted with 300 ml of water and extracted 3 times using in each case 150 ml of tert-butyl methyl ether. After the solvent had been evaporated, 6.4 g of the desired product was obtained as an oil. NMR (CDC13) ppm: 6.7 t (lH); 7.05-7.20 (2H); 755 [sic] -7.70 m (lH). c) 2-difluoromethoxy-6-flurobenzamidoxime A mixture of 6.4 g of 2-difluoromethoxy-6-flurobenzonitrile and 3.1 g of hydroxylamine hydrochloride, 2.6 g of sodium carbonate, 7 g of water and 35 ml of ethanol was stirred for 20 hours. hours at 75 ° C. After the solvent had been evaporated, the residue was separated between 40 ml of 2N HCl and 20 ml of ethyl acetate. After the HCl phase had been separated, it was brought to neutrality at pH 7 and extracted 3 times in each case with 40 ml of tert-butyl methyl ether, the solvent was evaporated. This produced 6.0 of the desired product. NMR (DMSO) ppm: 5.9 s (2H); 7.0-7.2 m (2H); 7.15 t (lH), 7.4-7.44 m (1H); 9.5 s (1H). d) 2-difluoromethoxy-6-flurobenzamide O-cyclopropylmethyl oxime 0.4 g of 80% pure sodium hydride was added to a solution of 3.0 g of 2-difluoromethoxy-6-luorobenzamidoxine in 30 ml of dimethylformamide, (DMF) at 0- 5 ° C, and the mixture was stirred at this temperature for 3 hours. 1.8 g of cyclopropylamine bromine were subsequently added at the same temperature, and the stirring was subsequently continued for 2 hours at 5 ° C and overnight at room temperature. The batch was stirred to 300 ml of water and extracted 3 times with 70 ml in each case of cyclohexane. After the cyclohexane had been evaporated, 1.9 g of the desired product was obtained. NMR (CDC13) ppm: 0.3 m (2H); 0.55 m (2H); 1.2 m (lH); 3.9 d (2H); 4.85 s, br (2H); 6.6 t (lH); 6.85-7.1 m (2H); 7.35-7.45 m (lH). e) N-Phenylacetyl-2-difluoromethoxy-6-flurobenzamide O-cyclopropylmethyloxime (Compound 1.6 of Table I). 1.9 g of 2-difluoromethaxy-6-flurobenzamide 0-cyclopropylmethyloxime, which had been obtained in step d), and 1.5 g of phenylacetyl chloride were refluxed for 20 hours together with 40 ml of toluene. After cooling 40 ml of water were added and the pH was brought to 11. After the solvent had been evaporated, the residue was subsequently subjected to column chromatography on silica gel with a 99: 1 mixture of cyclohexane and ethyl acetate. ethyl as the eluent, 1.6 g of the desired product from p. F. 58-60 ° C were isolated from the toluene phase. NMR (CDCl 3) ppm: 0.2 m (2H); 0.50 m (2H); 1.0 m (lH); 3.9 d (2H); 6.4 t (lH); 6.85-7.0 m (2H); 7.2-7.5 m (6H) 8.5 s (1H), N-Phenylacetyl-2-difluoromethoxy-6-flurobenzamide O-allylmethyloxime (Compound 1.3 of Table I) was obtained in a similar manner as an oil.

Example 2 - Preparation of 2-hydroxy-5,6-difluorobenzonitrile A) preparation of 2-methoxy-5,6-difluorobenzaldehyde oxime At 20-25 ° C, a solution of 29.4 g of 2-methoxy-5,6-difluoro -benzaldehyde (according to Example 27 of WO 97/03071) was added dropwise with stirring to a mixture of 16.0 g of hydroxylamine hydrochloride, 18.9 g of sodium acetate and 110 ml of an aqueous 90% methanol solution. %. The mixture was stirred for 16 hours, the methanol was evaporated, the mixture was made into a paste using 250 ml of water and then washed and dried, yielding 28.3 g of the desired product of p. F. 199-201 ° C. b) Preparation of 2-methoxy-5,6-difluorobenzonitrile 20 drops of dimethylformamide and 16.6 g of thionyl chloride were added to a suspension of 18.7 g of the product obtained according to a) in 100 ml of toluene, and care was taken that the temperature did not rise above 30 ° C. After 4 hours of stirring at 30 ° C, the toluene and thionyl chloride were evaporated under reduced pressure and 16.5 g of the desired product was isolated as an oil. NMR (CDCl 3) ppm: 3.9 s (3H); 6.65-6.75 (1H); 7.3-7.45 (1H). c) Preparation of 2-hydroxy-5,6-difluorobenzonitrile At 50 ° C, 21.7 g of AICI 3 were added little by little with stirring to a solution of 23.0 g of the product obtained according to b) in 70 ml of toluene. After the addition, the mixture was heated to reflux for 2 hours. After cooling, the reaction mixture was poured into 350 ml of water and adjusted to pH 1 using 2n HCl [sic]. The resulting crude product was extracted with tert-butyl methyl ether (2 x 100 mL) and purified by dissolving in 2N NaOH [sic] (2 x 80 mL) and acidification of the alkaline phase to pH 5 using 2N HCl [sic]. After extraction, with tert-butyl methyl ether (2 x 80 ml), drying and evaporation of the solvent, 19.9 g of the desired product was isolated as an oil. NMR (CDCl 3) ppm: 6.45s, brd (1H); 6-7-6.8m (1H); 7.25-7.4m (1H).

Example 3 Efficacy against dusty mildew of wheat Leaves of wheat seedlings cv. "Frühgold" grown in pots were sprayed to the point of condensation with the aqueous preparation of the active ingredient prepared with a standard solution composed of active ingredient 10%, cyclohexanone 63% and emulsifying agent 27% and, 24 hours, after the coating by spray had dried, sprinkled with dusty wheat mold spores (Erysiphe graminis, f.sp. tritici). The test plants were subsequently placed in the greenhouse at 20-22 ° C and relative atmospheric humidity of 75 to 80%. After 7 days the degree of mold development was determined visually as a percentage of the area of the total leaf.

The plants that had been treated with an aqueous preparation containing 63 ppm of the active ingredients 1.3, I. ' 1.9, 1.10, 1.12, 1.13, and 1.29 of Table 1 were free of disease while the disease level of untreated plants was 80%.

Example 3 [sic]: Efficacy against dusty wheat mold Leaves of wheat seedlings cv. "Frühgold" grown in pots were sprayed to the point of condensation with the aqueous preparation of the active ingredient prepared with a standard solution composed of active ingredient 10%, cyclohexanone 63% and emulsifier 27% and, 24 hours, after the coating by spray had dried, sprinkled with dusty wheat mold spores (Erysiphe graminis, f.sp. tritici). The test plants were subsequently placed in the greenhouse at 20-22 ° C and relative atmospheric humidity of 75 to 80%. After 7 days the degree of visual mold development was determined as a percentage of the area of the total leaf.

The plants that had been treated with the active ingredients 11.1 and II.3, of Table 2 were free of disease while the disease level of the untreated plants was 80%.

Claims (4)

1. A benzamidoxime derivative of the formula I wherein R 'is difluoromethyl or trifluoromethyl R' is hydrogen or fluorine R is C 1 -C 4 alkyl which can be substituted by cyano, C 1 -C haloalkyl, C 1 -C 4 alkoxy C 1 -C 4 alkyl, alkenyl C3-C6, C3-C6 haloalkenyl, C3-C6 alkynyl, C3-Cs cycloalkyl-C3-C4 alkyl "is phenyl C? -C? Alkyl, which may carry one or more substituents selected from the group consists of halogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy and C 1 -C 4 haloalkoxy in the phenyl ring, or is C 1 -C 4 alkyl thienyl which may carry one or more substituents selected from the group consisting of a group consisting of halogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy and C 1 -C 4 haloalkoxy in the thienyl ring, or is pyrazolyl C 1 -C 4 alkyl which can carry one or more selected substituents of the group consisting of halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy and C3 haloalkoxy .-- C4 in the pyrazole ring The benzamidoxime derivative of the formula I as mentioned in claim 1, wherein R is benzyl which can carry one to three substituents selected from the group consisting of halogen, C 1 -C 4 alkyl and C 1 -C 4 haloalkoxy on the phenyl ring. The benzamidoxime derivative of the formula I as mentioned in claim 1, wherein R is difluoromethyl. The benzamidoxime derivative of the formula I as mentioned in claim 1, wherein R is fluorine and is in the 5-position of the phenyl ring. A benzonitrile of formula III The benzonitrile of the formula III as mentioned in claim 5, wherein the fluorine atom is in the 5-position of the phenyl ring. A benzonitrile of formula IV i) wherein R1 and R2 are as defined in claim 1. 8. The benzonitrile of the formula IV as mentioned in claim VII, wherein R2 is fluorine and is in the 5-position of the phenyl ring. 9. A benzamidoxime of formula V wherein R 1 and R 2 are as defined in claim 1. 10. The benzamidoxime of the formula V as mentioned in claim 9, wherein R 2 is fluorine and is in the 5-position of the phenyl ring. 11. A benzamidoxime of formula VI wherein R 1, R 2 and R 3 are as defined in claim 1. 1

2. The benzamidoxime of the formula VI as mentioned in claim 11, wherein R is fluorine and is in the 5-position of the phenyl ring. 1

3. The use of the benzamidoxime derivative of the formula I as mentioned in any of claims 1-4 for controlling harmful fungi. A fungicidal composition containing an antifungally effective amount of at least one benzamidoxime derivative of the formula I as mentioned in any of claims 1-

4. A method for controlling harmful fungi, which consists of treating the harmful fungus, its habitat or the plants, areas, materials or spaces that must be kept free of these with an effective amount as a fungicide of a compound of the formula I or a fungicidal composition which contains a benzamidoxime derivative of the formula I as mentioned in claim 14. SUMMARY OF THE INVENTION The preparation of the benzamidoxime derivatives of the formula I is described wherein: Ri is difluoromethyl or trifluoromethyl ir is hydrogen or fluorine R ~ is C 1 -C alkyl which can be substituted by cyano, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy C 1 -C 4 alkyl, C 3 alkenyl -C6, C3-C3 haloalkenyl, O3-C6 alkynyl, C3-C8 cycloalkyl C1-C4 alkyl? it is phenyl C 1 -C 4 alkyl which may carry one or more constituents selected from the group consisting of halogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy and C 1 -C 4 haloalkoxy in the phenyl ring, or is thienyl C1-C4 alkyl which may carry one or more substituents selected from the group consisting of halogen, C1-C4 alkyl, C1-C4 haloalkyl, C1-C4 alkoxy and C1-C4 haloalkoxy in the thienyl ring or it is pyrazolyl C3-C4 alkyl which may carry one or more substituents selected from the group consisting of halogen, C1-C4 alkyl, C3-C4 haloalkyl, C1-C4 alkoxy and C1-C4 haloalkoxy in the pyrazole ring, and the intermediates for its preparation and its use as fungicides.