Derivatives benzamidoxime, intermediate products, antifungal agent, the method of combating phytopathogenic fungi

 

(57) Abstract:

Describes the new derivatives benzamidoxime formula (I), where R1- deformity, R2is hydrogen or fluorine, R3- C1-C4alkyl, C3-C6alkenyl,3-C6quinil,3-C8cycloalkyl-C1-C4alkyl, R4is phenyl WITH1-C6alkyl, in which phenyl ring may bear one or more substituents selected from the group comprising halogen, C1-C4alkyl, C1-C4alkoxy, or denotes thienyl1-C4alkyl. Also describes benzonitrile and benzamidoxime, which are intermediate products, as well as fungicidal agent-based compounds of formula (I) and a method of combating phytopathogenic fungi, using the compound of the formula (I) and a tool based on it. Effect: increased activity means 7 C. and 6 C.p. f-crystals, 5 PL.

The present invention relates to new derivatives benzamidoxime, to method and intermediate products for their preparation and their use as fungicides.

From JP-A 02/006453 with known fungicidal action derived benzamidoxime, which, however, is soedinenijam of this type.

Accordingly, the present invention was based on the task to obtain new derivatives benzamidoxime higher their efficiency, especially at low application rates.

Unexpectedly, it was found that derivatives benzamidoxime formula I

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where R1denotes deformity or trifluoromethyl,

R2denotes hydrogen or fluorine,

R3stands WITH1-C4alkyl which may be substituted by cyano, C1-C4halogenated,1-C4alkoxy-C1-C4alkyl, C3-C6alkenyl,3-C6halogenoalkanes,3-C6quinil,3-C8cycloalkyl - C1-C4alkyl,

R4denotes phenyl-C1-C6alkyl, in which phenyl ring may bear one or more substituents selected from the group comprising halogen, C1-C4alkyl, C1-C4halogenated,1-C4alkoxy and C1-C4halogenoalkane, or denotes thienyl-C1-C4alkyl, who thienyl ring may bear one or more substituents selected from the group comprising halogen, C1-C4alkyl, With1-C4alkyl, in which pyrazol ring may bear one or more substituents selected from the group comprising halogen, C1-C4alkyl, C1-C4halogenated,1-C4alkoxy and C1-C4halogenoalkane have more effective fungicidal action.

When specifying values of the substituents R1-R4used General concepts, including a group of compounds, namely:

halogen means fluorine, bromine, chlorine or iodine, especially fluorine or chlorine;

further, for example:

WITH1-C4alkyl represents methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl or 1,1-dimethylethyl, especially ethyl;

WITH1-C4halogenated represents a C1-C4the alkyl residue as defined above, substituted partially or totally fluorine, chlorine, bromine and/or iodine, for example, trichloromethyl, trifluoromethyl, 2-foretel, 2-chloroethyl, 2-bromacil, 2,2-dottorati, 2,2,2-triptorelin, 2,2,2-trichloroethyl, 2-forproper, 3-forprofit, 2-chloropropyl or 3-chloropropyl, primarily 2-foradil or 2-chloroethyl;

cyano-C1-C4alkyl represents, for example, cyanomethyl, 1-C is IDE just cyanomethyl or 2-cyanoethyl;

WITH1-C4alkoxy represents methoxy, ethoxy, n-propoxy, 1-methyl-ethoxy, n-butoxy, 1 methylpropoxy, 2-methylpropoxy or 1,1-dimethylmethoxy, especially methoxy or ethoxy;

WITH1-C4alkoxy-C1-C4alkyl is a substituted, as described above, WITH1-C4alkoxygroup1-C4alkyl, i.e., for example, methoxymethyl, ethoxymethyl, n-propoxymethyl, (1 methylethoxy)methyl, n-butoxymethyl, (1 methylpropoxy)methyl, (2-methylpropoxy)methyl, (1,1-dimethylmethoxy)methyl, 2-(methoxy)ethyl or 2-(ethoxy)ethyl, primarily methoxymethyl or 2-methoxyethyl;

WITH3-C6alkenyl represents, for example, prop-2-EN-1-yl, n-butene-4-yl, 1-methylprop-2-EN-1-yl, 2-methylprop-2-EN-1-yl or 2-butene-1-yl, especially prop-2-EN-1-yl;

WITH3-C6halogenoalkanes represents a C3-C6alkenyl, as noted above, partially substituted or fully fluorine, chlorine and/or bromine, such as 2-chloroallyl, 3-chloroallyl, 2,3-dichlorethyl or 3.3-dichlorethyl, primarily 2-chlorallyl;

WITH3-C6quinil represents, for example, prop-1-Jn-1-yl, prop-2-in-1-yl, n-but-1-in-1-yl, n-but-1-in-3-yl, n-but-1-in-4-yl or n-but-2-in-1-yl, especially prop-2-in-1-yl;

Ylmethyl, 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, primarily cyclopentylmethyl;

phenyl-C1-C6alkyl represents, for example benzyl, 1-phenylethyl, 2-phenylethyl, 1-phenylprop-1-yl, 2-phenylprop-1-yl, 3-phenylprop-1-yl, especially benzyl or 2-phenylethyl;

thienyl-C1-C4alkyl represents, for example 2-thienylmethyl, 3-thienylmethyl or 2-titilate;

pyrazole-C1-C4alkyl represents, for example 1-parasailer, 2-parasailer, 3-parasailer or 2-personility.

The particular efficiency, as a rule, in all cases showed compounds in which the substituent R1is deformity, Deputy R3is cyclopropylmethyl, and the substituent R4represents benzyl, which may carry phenyl ring from one to three substituents selected from the above group, especially one to three substituents selected from the group comprising fluorine, chlorine, methyl, methoxy and trifluoromethyl.

The most preferred include the link is uchenykh in table.1 and by the way, initially characterized as oil, given the NMR spectra and, accordingly, the melting temperature (see tab.1.1).

Proposed in the invention derived benzamidoxime formula I get the method according to the invention the cleavage of ethers fluorinated benzonitrile formula II, the interaction obtained benzonitrile formula III with haloalkanes CHmFnl (m denotes 0 or 1, and n denotes 2 or 3), such as CHF2Cl or CF3I, the primary environment (preferably in the presence of alkali metal hydroxide) to produce benzonitrile formula IV and the subsequent interaction of these benzonitrile IV with hydroxylamine or its salts in aqueous solution, preferably in water or in water-alcohol mixtures, not necessarily in the presence of a base, resulting in benzamidoxime formula V, which are then by known techniques alkylate with getting forproducts formula VI.

Benzamidoxime formula VI can then by known techniques to allievate the corresponding acid halides, preferably acid chlorides of the acids, by heating in an inert solvent (preferably to temperatures in the range from 20 d is of icela enough to call additional area primarily hydrocarbons or ethers, particularly preferably aromatic hydrocarbons, such as toluene or xylene.

R1to the reaction scheme shown in the end of the description, is a grouping of CHmFnwhere m denotes 0 or 1, and n denotes 2 or 3.

Indicated in the diagram above, the intermediate products of the formula III in which R denotes fluorine, as well as intermediates of the formulae IV, V and VI, are new compounds and are another object of the present invention. The process of obtaining these new intermediate products with giftory substitution can be made on the basis of 2,3-debtor-6-methoxybenzaldehyde (which can be obtained, for example, by the method according to example 27 in the international application WO 97/03071) as described in example 2 variants up to the stage of the compounds of formula IV inclusive. Further operations to obtain the corresponding compounds of formulas V and VI skilled in the art will known.

It preferred are such compounds of formulas IV, V and VI, in which R2and R3(compound VI) have the same values as above for compounds of formula I.

Preferred compounds of formula IV are presented in table. 3.

In table. 4 presents some preferred compounds of formula VI.

The compounds of formula I differ extremely high efficacy against a broad spectrum of phytopathogenic fungi, especially from the classes of records of Ascomycetes, deuteromycetes, phykomycets and basidiomycetes. They are partly systemic action and can therefore be used as fungicides for treatment of leaves and soil. Usually the plants are sprayed with either opilivayut active substances or so to handle the seeds of the respective plants.

Composition of active substances prepared by known techniques, for example, diluting the active substances with solvents and/or introducing additives fillers, optionally using emulsifiers and dispersants, and in the case of using water as a diluent, and may use other organic solvents, servants auxiliary agents dissolution. As auxiliary substances for these purposes can be considered mainly the following: solvents such as aromatics (e.g. xylene), chlorinated aromatics (e.g., Harbison), amines (e.g. ethanolamine, dimethylformamide) and water; fillers such as natural flour rocks (for example, kaolin, alumina, talc, chalk) and synthetic flour rocks (for example, highly dispersed silicic acid, silicates); emulsifiers such as nonionic and anionic emulsifiers (for example, ethers of polyoxyethylene and fatty alcohols, alkyl sulphonates and arylsulfonate), and dispersing agents, such as exhaust ligninolytic liquor or methylcellulose.

As surface-active substances can be used salts of alkali, alkaline earth metal and ammonium salts of aromatic sulfonic acids, for example lignin-, phenol-, naftalin dibutylaminoethanol, as well as salts of fatty acids, alkyl - and alkylarylsulfonates salt, alkylsulfate salts, sulfate salts ethers laurinovoj acid and sulfate salts of fatty alcohols, further, salts of sulfated hexa-, hepta - and octadecanol, in addition, glycol fatty acid esters, condensation products of sulfonated naphthalene and its derivatives with formaldehyde, condensation products of naphthalene, respectively naphthalenesulfonic with phenol and formaldehyde, simple live polyoxyethylenated is a, alkylaminocarbonyl, isotridecyl alcohol, condensates of fatty alcohols and ethylene oxide, ethoxylated castor oil, polyoxyethyleneglycol ether or polyoxypropylene, acetate polyglycolide ester lauric alcohol, complex sorbitol esters, exhaust ligninolytic liquor or methylcellulose.

Powder medications for dusting and dusting can be prepared by mixing or joint grinding of active substances with a solid filler.

The granules such as pellets in the shell, impregnated granulates and homogeneous granulates can be obtained by linking the active substances with solid fillers. Such solid supports can serve as mineral lands, in particular silica gel, silicic acid, diatomaceous earth, silicates, talc, kaolin, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium sulfate and magnesium, magnesium oxide, ground synthetic materials, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, urea and vegetable products such as grain flour, flour from tree bark, wood flour and flour from a nutshell, pulp p is I. A solution of 90 wt. parts of the compound I according to the invention and 10 wt. parts N-methyl-2-pyrrolidone, designed for use in the form of tiny droplets.

II. A mixture of 10 wt. parts of the compound I according to the invention, 70 wt. parts of xylene, 10 wt. parts of the product of the merger 8-10 moles of ethylene oxide to 1 pray N-monoethanolamide oleic acid, 5 wt. parts of the calcium salt dodecylbenzenesulfonic acid, 5 wt. parts of the product of the joining of 40 moles of ethylene oxide to 1 pray castor oil; after a thin uniform distribution of solution in the water receive the corresponding variance.

III. Aqueous dispersion of 10 wt. parts of the compound I according to the invention, 40 wt. parts of cyclohexanone, 30 wt. parts of Isobutanol, 20 wt. parts of the product of the joining of 40 moles of ethylene oxide to 1 pray castor oil.

IV. Aqueous dispersion of 10 wt. parts of the compound I according to the invention, 25 wt. parts of cyclohexanol, 55 wt. parts of the fraction of oil produced during the refining of oil, with a boiling point 210-280oC and 10 wt. parts of the product of the joining of 40 moles of ethylene oxide to 1 pray castor oil.

V. Milled in a hammer mill, a mixture of 80 wt. parts of the compound I according to the invention, the sodium salt of ligninsulfonate from spent sulfite liquor and 7 wt. parts of powdered silica gel; after a thin uniform distribution of the mixture in water to obtain a solution for spraying.

VI. Homogeneous mixture of 3 wt. parts of the compound I according to the invention and 97 wt. parts of fine kaolin; this drug for dusting contains 3 wt.% the active substance.

VII. Homogeneous mixture of 30 wt. parts of the compound I according to the invention, 62 wt. parts of powdered silica gel and 8 wt. parts of paraffin oil deposited on the surface of the gel; this composition gives the current substance good adhesive ability.

VIII. Stable aqueous dispersion of 40 wt. parts of the compound I according to the invention, 10 wt. parts of the sodium salt of the condensation product of phenolsulfonate-urea-formaldehyde, 2 wt. parts of silica gel and 48 wt. parts of water, which can be diluted further.

IX. A stable oily dispersion of 20 wt. parts of the compound I according to the invention 2 wt. parts of the calcium salt of dodecylbenzenesulfonate, 8 mass. parts polyglycolic ether fatty alcohol, 20 wt. parts of the sodium salt of the condensation product of phenolsulfonate with urea and formaldehyde and 50 wt. parts of the, the new compounds are distinguished exceptionally high efficacy against a broad spectrum of phytopathogenic fungi, especially from the classes of deuteromycetes, records of Ascomycetes, phykomycets and basidiomycetes. They are partly systemic action and can be used as fungicides for treatment of leaves and soil.

They have a special importance to deal with the numerous mushrooms, affecting various cultivated plants, such as wheat, rye, barley, oats, rice, maize, lawns, cotton, soybeans, coffee, sugar cane, grapes, fruit and ornamental plants, vegetable crops, such as cucumbers, beans and pumpkin, as well as affecting the seeds of these plants.

The principle of using compounds according to the invention is that the mushrooms or require protection from destruction of their seeds, plants, materials or the soil are treated fungicide active number of active substances. Such processing is carried out before or after infection of the materials, plants or seeds by the fungi.

The new compounds are particularly suitable for dealing with the following plant diseases: Erysiphe graminis (powdery mildew) on cereals, Erysiphe cichoracearum and Sphaerotheca fuliginea on Cucurbitaceae, Podosphaera leuc, the Ustilago species on cereals and sugar cane, Venturia inaequalis (scab) on apples, Helminthosporium species on cereals, Septoria nodorwn on wheat, Botrytis cinerea (grey mould) on strawberries, grape vines, ornamental plants and vegetable crops, Pseudocercosporella herpotrichoides on wheat and barley, Pyricularia oryzae on rice, Phytophthora infestans on potatoes and tomatoes, Fusarium species and Verticillium on different crops, Plasmopara viticola on grape vines, Alternaria species on vegetables and fruit crops.

The new compounds can also be used to protect materials (wood protection), for example, against the fungus Paecilomyces variotii.

Fungicidal agent containing, as a rule, from 0.1 to 95, preferably from 0.5 to 90 wt.% the active substance.

Consumption rates depending on what effect I want to get ranges from 0.025 to 2.0 kg of active substance per hectare, preferably from 0.1 to 1 kg/ha

Seed treatment active ingredients should be used, generally in amounts of from 0.001 to 50 g, preferably from 0.01 to 10 g per kilogram of seed.

Proposed according to the invention means in their use as fungicides may also be used together with other active substances, for example with geogie fungicides in many cases reach the extension of the spectrum of fungicidal action.

Below is a list of fungicides together with which can be applied compounds according to the invention, this list serves to illustrate such combinative capabilities and in no way limits the scope of the invention. Such acomponent mixtures include:

sulfur, dithiocarbamates and their derivatives, such as peridomiciliary, zinc dimethyldithiocarbamate, ethylenebisdithiocarbamate zinc, ethylenebisdithiocarbamate manganese, ethylenediaminediacetic manganese-zinc, tetramethylthiourea, ammonia complex (N, N-ethylenebisdithiocarbamate) zinc ammonium complex (N,N'-propyltrimethylammonium) zinc (N,N'-propyltrimethylammonium) zinc, N,N'-polypropylenes(thiocarbamoyl-yl)disulphide;

nitro-derivatives, such as dinitro-(1-methylheptan)phenylketone, 2-sec-butyl-4,6-dinitrophenyl-3,3-dimethylacrylate, 2 sec-butyl-4,6-dinitrobenzophenone, diisopropyl ether 5-nitroisophthalic acid;

heterocyclic substances, such as 2-heptadecyl-2-imidazoline, 2,4-dichloro-6-(o-chloroanilino)-s-triazine, O, O-diethylthiophosphoryl, 5-amino-1-[bis-(dimethylamino)phosphinyl] -3-phenyl-1,2,4-triazole, 2,3-dicyano-1,4-dicyandiamide, 2-thio-1,3-dithiolo [4,5-b] Hinojosa, 2-(furyl-(2))-benzimidazole, 2-(thiazolyl-(4)) -benzimidazole, N-(1,1,2,2-tetrachloroethylthio)tetrahydrophthalate, N-trichloromethylpyridine, N-trikhlormyetilsilanye;

diamid N-dichloromethylene-N',N'-dimethyl-N-fanilstroi acid, 5-ethoxy-3-trichloromethyl-1,2,3-thiadiazole, 2-regenmeister, 1,4-dichloro-2,5-dimethoxybenzene, 4-(2-chlorophenylhydrazone)-3-methyl-5-isoxazolone, pyridine-2-thio-1-oxide, 8-hydroxyquinoline, according to its copper salt, 2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiin, 2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiin-4,4-dioxide, anilide 2-methyl-5,6-dihydro-4H-Piran-3-carboxylic acid, anilide 2-methylfuran-3-carboxylic acid, anilide 2.5-dimethylfuran-3-carboxylic acid, anilide 2,4,5-trimethylphenyl-3-carboxylic acid, cyclohexylamine 2.5-dimethylfuran-3-carboxylic acid amide N-cyclohexyl-N-methoxy-2,5-dimethylfuran-3-carboxylic acid, anilide 2-methylbenzoic acid, anilide 2-iodobenzoyl acid, N-formyl-N-morpholine-2,2,2-trichloroacetyl, piperazine-1,4-diylbis(1-(2,2,2-trichlorethyl)formamide, 1-(3,4-dichloraniline)-1-formylamino-2,2,2-trichloroethane, 2,6-dimethyl-N-tredecillion, respectively, its salts, 2,6-dimethyl-N-cyclododecyl, respectively, its salts, N-[3-(p-tert-butylphenyl)-2 methylpropyl the-2-ileti] -1H-1,2,4-triazole, 1[2-(2,4-dichlorophenyl)-4-n-propyl-1,3-dioxolane-2-ileti] -1H-1,2,4-triazole, N-(n-propyl)-N-(2,4,6-trichlorophenoxy) N'-imidazolidine, 1-(4-chlorphenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazole-1-yl)-2-butanone, (2-chlorophenyl)-(4-chlorophenyl)-5-pyrimidinemethanol, 5-butyl-2-dimethylamino-4-hydroxy-6-methylpyrimidine, bis(p-chlorophenyl)-3-pyridinemethanol, 1,2-bis(3-etoxycarbonyl-2-touraid)benzene, 1,2-bis(3-methoxycarbonyl-2-touraid)benzene, [2-(4-chlorophenyl)ethyl] -(1,1-dimethylethyl)-1H-1,2,4-triazole-1-ethanol, 1-[3-(2-chlorophenyl)-1(4-forfinal)oxiran-2-ylmethyl] -1H-1,2,4-triazole; and

various fungicides, such as dodecylguanidine, 3-[3-(3,5-dimethyl-2-oxocyclohexyl) -2-hydroxyethyl] glutarimide, hexachlorobenzene, DL-methyl-N-(2,6-dimetilfenil)-N-furoyl(2)-alanine, methyl ester of DL-N - (2,6-dimetilfenil)-N(2'-methoxyacetyl)alanine, N - (2,6-dime-terphenyl)-N-chloroacetyl-DL-2-aminobutyrate, methyl ester of DL-N-(2,6-dimetilfenil)-N-(phenylacetyl)alanine, 5-methyl-5-vinyl-3-(3,5-dichlorophenyl)-2,4-dioxo-1,3-oxazolidine, 3-[3,5-dichlorophenyl-(5-methyl-5-methoxymethyl]-1,3-oxazolidin-2,4-dione, 3-(3,5-dichlorophenyl)-1-isopropylcarbodiimide, imide N-(3,5-dichlorophenyl)-1,2-dimethylcyclopropane-1,2-dicarboxylic acid, 2-cyano-[N-(acylaminoalkyl)-2-methoxyimino] ndimethylacetamide, 1-[2-(2,4-dichlorophenyl)pentyl]-1H-1,2,4-triazole, 2,4-gift the aminopyridine, 1((bis(4-forfinal)methylsilyl)methyl)-1H-1,2,4-triazole;

strobilurin, such as methyl-o-methoxyimino-[a-(o-tolyloxy)-o-tolyl] acetate, methyl-E-2{ 2[6-(2-cianfrocca)pyrimidine-4-yloxy] phenyl} -3-ethoxyacrylate, methyl-o-methoxyimino[-(2,5-dimethylphenoxy)-o-tolyl] ndimethylacetamide;

anilinopyrimidines, such as N-(4,6-dimethylpyrimidin-2-yl)aniline, N - [4-methyl-6-(1-PROPYNYL)pyrimidine-2-yl] aniline, N-(4-methyl-6-cyclopropylamino-2-yl) aniline

phenylpyrrole, such as 4-(2,2-debtor-1,3-benzodioxol-4-yl)pyrrole-3-carbonitrile;

amides of cinnamic acid, such as morpholin 3-(4-chlorophenyl)-3-(3,4-acid)acrylic acid.

Example 1

a) 6-fluoro-2-hydroxybenzonitrile

7,8 g 2-methoxy-6-perbenzoate and 18 g of pyridinecarboxamide was heated in a dry nitrogen atmosphere for 5 h to 195oC. After cooling, the mixture was distributed between 50 ml water and 50 ml of tert-butyl methyl ether and then the organic phase was extracted with 40 ml of 2 N. NaOH. The alkaline extract was adjusted at pH 5 and then was extracted twice respectively with 40 ml tert-butyl methyl ether. After evaporation of the solvent obtained 4.7 g of the desired product as oil (IHVR: 93%).

NMR (DMSO) frequent. /million: 6,8-6,95 m (2H); 7.5 to 7,6 m (1H); 11,8 s, Shir. (methoxyethane and 25 ml of NaOH (33%) under stirring was applied at the 75oWith 6.3 g of Chlorodifluoromethane (the reflux condenser was cooled with dry ice) and continued to stir for 1 h at 70-75oC. After cooling, the mixture was diluted with 300 ml of water and was extracted three times respectively in portions of 150 ml tert-butyl methyl ether. After evaporation of the solvent obtained 6.5 g of the desired product in the form of butter.

NMR (CDCl3) part./million: 6,7 t (1H); 7,05-7,20 m (2H); 7,55-7,70 m (1H).

C) 2-deformedarse-6-forbesautos.com

A mixture of 6.4 g of 2-deformedarse-6-perbenzoate and 3.1 g of hydroxylamine hydrochloride, 2.6 g of sodium carbonate, 7 ml of water and 35 ml of ethanol was stirred for 20 h at 75oC. After evaporation of the solvent the residue was distributed between 40 ml of 2 N. Hcl and 20 ml of ethyl acetate. After separation of the Hcl-phase, neutralizing to pH 7 and the three-fold extraction with 40 ml tert-butyl methyl ether, respectively, the solvent is evaporated. Thus obtained 6.0 g of the desired product.

NMR (DMSO) ppm million: 5,9 s (2H); 7,0-7,2 m (2H); 7,15 t (1H); 7,4-7,44 m (1H); 9,5 s (1H).

g) 2-deformedarse-6-perbenzoic[O-cyclopropylmethyl]oxime.

To a solution of 3.0 g of 2-deformedarse-6-forbesautos.com in 30 ml of dimethylformamide (DMF) at 0-5oWith added 0.4 g of 80%-leg bromocyclopropane, then the stirring was continued for 2 h at 5oC and overnight at room temperature. Then this mixture with vigorous stirring was diluted with 300 ml of water and was extracted three times respectively portions 70 ml of cyclohexane. After evaporation of the solvent was obtained 1.9 g of the desired product.

NMR (DCl3) part./million: 0,3 m (2H); 0,55 m (2H); 1.2 m (1H); 3.9 to d (2H); 4,85 s, Shir. (2H); 6,6 t (1H); 6,85-7,1 m (2H); 7,35-7,45 m (1H).

d) N-phenylacetyl-2-deformedarse-6-perbenzoic[O-cyclopropylmethyl]oxime (compound I. 6 of table. 1)

1.9 grams obtained in stage g), 2-deformedarse-6-perbenzoic-[O-cyclopropylmethyl] oxime and 1.5 g of the acid chloride phenylacetic acid was heated with 40 ml of toluene for 20 h under reflux. After cooling, was added 40 ml of water and was adjusted at pH 9. From the toluene phase after evaporation of the solvent and subsequent column chromatography on silica gel using as eluents mixture of cyclohexane and ethyl acetate in a ratio of 99:1 was provided 1.6 g of the target product with tPL58-60oC.

NMR (DCl3) part./million: 0,2 m (2H); 0,50 m (2H); 1,0 m (1H); 3.9 to d (2H); 6,4 t (1H); 6,85-7,0 m (2H); 7,2-7,5 m (6H); 8,5 s (1H).

In a similar way received N-phenylacetyl-2-debtor the s 2-hydroxy-5,6-difterential

a) Obtaining 2-methoxy-5,6-differentiallock

To a mixture of 16 g of hydroxylamine hydrochloride, to 18.9 g of sodium acetate and 110 ml of 90% aqueous methanol with stirring was added dropwise at 20-25oTo a solution of 29.4 g of 2-methoxy-5,6-diferentialglea (according to example 27 from the application WO 97/03071). After stirring for 16 h and evaporation of methanol, rubbing with 250 ml of water to form a paste, rinsing, and drying got to 28.3 g of the desired product with tPL199-201oC.

b) Obtaining 2-methoxy-5,6-difterential

To a suspension of 18.7 g obtained in stage a) of the product in 100 ml of toluene was added 20 drops of dimethylformamide and 16.6 g of thionyl chloride, followed by the fact that the temperature did not exceed 30oC. After stirring for 4 h at 30oWith, evaporation under vacuum, toluene and thionyl chloride were allocated 16.5 g of the desired product in the form of butter.

NMR (DCl3) part./million: 3,9 s (3H); 6,65 to 6.75 m (1H); 7.3 to 7,45 m (1H).

C) Obtaining 2-hydroxy-5,6-difterential

To a solution of 23 g obtained in stage b) of the product in 70 ml of toluene at 50oPortions were added with stirring to 21.7 g ll3. Upon completion of the process of adding heated for 2 h with Oli pH to a value of 1. Thus obtained crude product was twice extracted with 100 ml of tert-butyl methyl ether, respectively, and was purified by dissolving in 2 N. NaOH (g ml) and acidification of the alkaline phase 2 N. Hcl to pH 5. After extraction tert-butylmethylamine ether (CH ml), drying and evaporation of the solvent allocated to 19.9 g of the desired product in the form of butter.

NMR (CDCl3) frequent. /million: 6,45 s, Shir. (1H); 6,7-6,8 m (1H); 7,25 to 7.4 m (1H).

Example 3: Effect against powdery mildew of wheat

Leaves grown in pots of seedlings of wheat varieties "Fruegold" intensively, until the drops were sprayed water composition of active ingredients, prepared from a source solution containing 10% active ingredient, 63% of ciculation and 27% of emulsifier and after 24 h after drying of the spray liquid was apilevel spores of powdery mildew of wheat (Erysiphe graminis f.sp.tritici). Then the experimental plants were placed in a greenhouse, where they are kept at a temperature in the range of 20-22oC and 75-80% relative humidity. After 7 days was visually determined as a percentage of the degree of the damage by the fungus total surface area of leaves. It was found that plants treated with water Compostela 63 frequent. /million, were not affected, whereas the degree of infestation of the untreated plants had reached 80%.

Example 4: Effect against powdery mildew of wheat

Leaves grown in pots of seedlings of wheat varieties "Fruegold" intensively, until the drops were sprayed water composition of active ingredients, prepared from a source solution containing 10% active ingredient, 63% of ciculation and 27% of emulsifier and after 24 h after drying of the spray liquid was apilevel spores of powdery mildew of wheat (Erysiphe graminis f.sp.tritici). Then the experimental plants were placed in a greenhouse, where they are kept at a temperature in the range of 20-22oC and 75-80% relative humidity. After 7 days was visually determined as a percentage of the degree of the damage by the fungus total surface area of leaves. It was found that plants treated with the aqueous composition of active substances, containing, respectively, of compound II.1 and II. 3 in the table, were not affected, whereas the degree of infestation of the untreated plants had reached 80%.

Derivatives benzamidoxime formula I

< / BR>
where R1denotes deformity,

R2denotes hydrogen or fluorine,
8cycloalkyl-C1-C4alkyl,

R4indicates the phenyl WITH1-C6alkyl, in which phenyl ring may bear one or more substituents selected from the group comprising halogen, C1-C4alkyl, C1-C4alkoxy, or denotes thienyl1-C4alkyl.

2. Derivatives benzamidoxime formula I on p. 1, where R4represents benzyl, which may carry phenyl ring from one to three substituents selected from the group comprising halogen, C1-C4alkyl and C1-C4alkoxy.

3. Derivatives benzamidoxime formula I on p. 1, where R2represents fluorine and is in position 5 of the phenyl ring.

4. Benzonitrile formula III

< / BR>
5. Benzonitrile formula III under item 4, where the fluorine atom is in position 5 of the phenyl ring.

6. Benzonitrile formula IV

< / BR>
where R1and R2have the values listed in paragraph 1.

7. Benzonitrile formula IV under item 6, where R2represent fluorine and is located in position 5 of the phenyl ring.

8. Benzamidoxime formula V

< / BR>
where R1and R2have the values listed in paragraph 1.

the ring.

10. Benzamidoxime formula VI

< / BR>
where R1denotes deformity,

R2denotes hydrogen or fluorine,

R3represents C3-C8cycloalkyl-C1-C4alkyl.

11. Benzamidoxime formula VI under item 10, where R2represents fluorine and is in position 5 of the phenyl ring.

12. Fungicidal agent containing in its composition fungicide effective amount of at least one derivative benzamidoxime formula I according to any one of paragraphs. 1-3.

13. A method of combating phytopathogenic fungi, wherein the fungi, their habitat or require protection from destruction of their plants, areas, materials or spaces treated fungicide effective amount of compounds of General formula I or fungicidal agent under item 12, containing in its composition derived benzamidoxime formula I.

 

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