Derivatives of benzimidazole and intermediate compounds for their production

 

(57) Abstract:

Usage: in agriculture as a fungicide. The essence of the invention: benzimidazole derivatives f-l (1 and 2). Connection f-l (3 - 5), where R is cyano or thiocarbamoyl; Q is lower alkyl or the group NQ1Q2where Q1and Q2independently lower alkyl, lower alkyl substituted by phenyl, or lower quinil, or Q1and Q2taken together with the nitrogen atom form patentino nitrogen-containing ring which may include an oxygen atom; X is hydrogen or halogen; Z is a group of f-crystals (O)n(CF2)m(O)p(CY2)qO5where n, p, s is 0 or 1 and are the same or different values; m is 1 or 2; q is 0 or 1, provided that when q is 0, both p and s is not equal to 1 at the same time; Y is the same or different and represent H, F, Cl, provided that CY2not a CCl2while Z together with two adjacent carbon atoms of the benzene ring forms a five-, six-membered cycle; B-CN or CCl3; X1-halogen; A group of NO2or NH22 S. and 3 C.p. f-crystals, 13 tables.

The invention relates to benzimidazole derivative and intermediate compounds for their preparation and can be used in rural households is t, mannosebinding, which are widely used as active ingredient for agricultural and horticultural fungicides as controlling agents for such diseases as late blight and powdery mildew.

However, these pesticides are not always effective as an active ingredient for agricultural and horticultural fungicides.

The aim of the invention is the finding compounds with excellent efficacy against fungal diseases and low phytotoxicity.

Offer benzimidazole derivative has excellent preventive and therapeutic efficacy against plant diseases, as well manifests itself in system activity and has no phytotoxicity.

In accordance with the present invention offers a benzimidazole derivative of the formula

Z

(1) where R is cyano or thiocarbamoyl;

Q is lower alkyl or a group represented by the formula Q1Q2where Q1and Q2independently lower alkyl, lower alkyl substituted by phenyl, or lower quinil, or Q1and Q2taken together with the nitrogen atom form a five - or six-membered nitrogen-containing ring, which optionally may include an oxygen atom;

the s where n, p. s is 0 or 1 and are the same or different values;

m is 1 or 2, 0 or 1, provided that when q is 0, or R and s is not equal to 1 at the same time; Y is the same or different and represent H, F, Cl, provided that SU2not a CCL2while Z together with two adjacent carbon atoms of the benzene ring forms a five - and six-membered cycle.

It is also proposed benzimidazole derivative of the formula

ZB

(2)

where X and Z have the above meanings;

In this JV or CCL3.

Intermediate compounds for the synthesis of these benzimidazole derivatives are compounds of the formula

where X1halogen; And a group of NO2or NH2,

< / BR>
Derivatives of benzimidazole of the formula (1) in which R is cyano, can be obtained by reaction of the compound 2-cyanobenzylidene formula

ZCN

with the derived sulfonyl chloride formula

Cl SO2Q (3)

In this reaction, the reaction temperature is maintained generally in the range from room temperature to the temperature of heating under reflux of the solvent and the reaction time in the range from instant to 24 hours, the Reaction is carried out in the presence of a base. Examples of usable bases are tertiary amination, sodium hydroxide, potassium hydroxide, potassium carbonate) and other. Regarding the amounts of reagents used for the reaction, the amount derived sulfonyl chloride of the formula (3) is usually 1-3 mol per mol of 2-cyanobenzylidene formula (2), and the number of bases 1 to 7 mol per mol of compound 2.

This reaction is carried out in the presence of a solvent. Specific examples of solvents are aliphatic hydrocarbons (e.g. hexane, petroleum ether), aromatic hydrocarbons (e.g. benzene, toluene), halogenated hydrocarbons (e.g. chloroform, dichloroethane), ethers (e.g. diethyl ether, dioxane, tetrahydrofuran), ketones (e.g. acetone, methyl ethyl ketone), esters (e.g. ethyl acetate, diethylmalonate), NITRILES (e.g. acetonitrile, isobutyronitrile), amides (for example, formamide, N,N-dimethylformamide), sulfur compounds (e.g., dimethyl sulfoxide and mixtures thereof.

After completion of the reaction, the reaction solution is subjected to ordinary post-treatment such as extraction with organic solvents, washing with water, concentration of the organic layer under reduced pressure, etc., and then the obtained product is purified, if necessary, t CLASS="ptx2">

Among these compounds, benzimidazole derivatives of the formula (1) in which R-thiocarbamoyl, are obtained by reaction of derivatives of 2-cyanobenzylidene formula (1) in which R is cyano, hydrogen sulfide. In this reaction, the reaction time is usually in the range from instant to 24 hours, and the reaction temperature from 0 to 70aboutC. This reaction is usually conducted in the presence of a base. Specific examples of the base are organic bases such as pyridine, triethylamine, diethylamine and so on, Although the solvent is not always required in this reaction, if necessary can be used. The solvent may be an ether, such as dioxane, tetrahydrofuran, etc. regarding the amounts of reagents used in this reaction, the amount of each sulfide and the base is usually from 1 mole to excess per mole of the derivative 2-cyanobenzylidene.

Among the compounds 2-cyanobenzylidene formula (2) those that do not have an axis of symmetry WITH2demonstrate the tautomerism as shown in the formula

ZCN ZCN

(4) where X and Z are defined above. Therefore, the receipt of these compounds with the use of these compounds in this way gives one of the compounds of formulas

ZR

(5)
2these compounds of formula (1) obtained from them can be attributed to one of the compounds having formulas (5) and (6), or a mixture thereof.

In these compounds, where Z forms a five-membered ring together with two carbon atoms benzilovogo ring, Z can be expressed as-A1AND2- A3-. If a1AND2AND3and a3AND2AND1asymmetrical to each other (for example, as in the case when Z-CF2CF2O-) connection with formula (1) contain two isomers having the formula

AR

(7)

AR

(8) where X, R and Q are defined above, each of the A1AND2and a3that may be the same or different, represents one atom or atomic group that meets the preceding definition of Z, and A1A2A3and A1A2A3different from each other. Each of these isomers and their mixtures are also included in the present connection.

If Z forms a six-membered ring together with two carbon atoms benzilovogo ring, Z can be expressed as-IN1IN2IN3IN4-. If1IN2IN3IN4and IN4IN3IN2IN1asymmetrical to each other (for example, as in the case when Z-OCF2C is defined above, each of the IN1IN2IN3and IN4that may be the same or different, represents one atom or atomic group that meets the preceding definition of Z, and1IN2IN3IN4and IN4IN3IN2IN1different from each other. Each of these isomers and their mixtures are included in the present connection.

Connection 2-cyanobenzylidene - the source material for the production of these compounds having the formula (2), are obtained by reaction of 2-(trichloromethyl)benzimidazole of the formula

ZCCl3< / BR>
(11) where X and Z are defined above, with ammonia.

In this reaction, the reaction temperature is maintained generally in the range from -30aboutWith up to the temperature of heating under reflux of the solvent and the reaction time varies from instant to 24 hours as to the amount of reagent used for the reaction, the amount of ammonia is from 6 mol to a large excess per mole of 2-(trichloromethyl)benzimidazole of the formula (11).

This reaction is usually conducted in the presence of a solvent. Specific examples of solvents are aliphatic hydrocarbons (e.g. hexane, petroleum ether), aromaticheskiye (Napier, diethylether, dioxane, tetrahydrofuran), ketones (e.g. acetone, methyl ethyl ketone), esters (e.g. ethyl acetate, diethylmalonate), NITRILES (e.g. acetonitrile, isobutyronitrile), amides (for example, formamide, N,N-dimethylformamide, sulfur compounds (e.g., dimethylsulfoxide), alcohols (e.g. methanol, ethanol, 2-propanol), water and mixtures thereof. After completion of the reaction, the reaction solution is neutralized with inorganic acid, for example hydrochloric acid, and then subjected to post-treatments such as extraction with organic solvents, washing with water, concentration of the organic layer, etc. So you can get the desired connection.

The compound 2-(trichloromethyl)benzimidazole of the formula (11) can be obtained by the reaction of o-phenylenediamine of the formula

Z

(12) where X and Z are defined above, with a compound of trichloroacetimidate formula

NH

II

CCl3COR1(13) where R1lower alkyl.

In this case, the reaction temperature is usually maintained in the range from -30aboutWith up to the temperature of heating under reflux of the solvent and the reaction time from instant to 24 hours-Number of trichloroacetimidate formula (13) is 1-2 mol per mol of o-phenylenedimaleimide are aliphatic hydrocarbons (for example, hexane, petroleum ether), aromatic hydrocarbons (benzene, toluene), halogenated hydrocarbons (e.g. chloroform, dichloroethane), ethers (for example, diethylether, dioxane, tetrahydrofuran), ketones (e.g. acetone, methyl ethyl ketone), NITRILES (e.g. acetonitrile, isobutyronitrile), amides (for example, formamide, N, N-diphenylformamidine), sulfur compounds (e.g., dimethylsulfoxide), alcohols (e.g. methanol, ethanol, 2-propanol), organic acids (e.g. formic acid, acetic acid, propionic acid) and mixtures thereof.

After completion of the reaction, the reaction solution is subjected, for example, post-processing, such as pouring into ice-cold water and separation of the resulting crystals by filtration or extraction with organic solvents, washing with water, concentration, etc., Then the resulting product is optionally purified by such operations as chromatography, recrystallization, etc., in affect, you can get the desired connection.

The compound 2-(trichloromethyl)benzimidazole of the formula (11) can also be obtained by reaction of o-phenylenediamine of the formula (12) with trichloroacetamido to obtain 2-aminoglutethimide and exposure to the latest cyclization reaction. In this Rea is varicela, reaction time from instant to 24 hours

This reaction is usually conducted in the presence of a solvent. Specific examples of solvents used for the reaction are aliphatic hydrocarbons (e.g. hexane, petroleum ether), aromatic hydrocarbons (e.g. benzene, toluene), halogenated hydrocarbons (e.g. chloroform, dichloroethane), ethers (for example, diethylether, dioxane, tetrahydrofuran), ketones (e.g. acetone, methyl ethyl ketone), esters (e.g. ethyl acetate, diethylmalonate), NITRILES (e.g. acetonitrile, isobutyronitrile), amides (for example, formamide, N, N-diphenylformamidine), sulfur compounds (e.g., dimethylsulfoxide), alcohols (e.g. methanol, ethanol, 2-propanol), water and mixtures thereof.

The reaction of o-phenylenediamine of the formula (11) with trichloroacetamido can be the same as the reaction of 2-cyanobenzylidene formula (2) with sulphonylchloride formula (3).

Derived o-phenylenediamine of the formula (12) can be obtained by the recovery of o-nitroaniline with the formula

Z

(14) where X and Z are defined above.

The recovery method, which can be used, carried out using sodium sulfide or acidic sodium sulfide in a mixture of water the heating under reflux of the solvent and the reaction time is within 12 hours In addition, this recovery can be performed by a method using powders of iron, zinc or tin in a mixture of water, organic acids (e.g. acetic acid) or inorganic acid (e.g. hydrochloric acid, sulfuric acid). The reaction is usually performed at 30-100aboutWithin 12 hours you Can also use the method of conducting the hydrogenation in the range from 0 to 60aboutWith under normal pressure or under pressure using a catalyst (such as platinum dioxide, palladium-carbon) in an organic solvent (e.g. ethanol, ethyl acetate).

Connection o-phenylenediamine of the formula (12) can also be obtained by reduction of compound o-dinitro formula

Z

(15)

where X and Z are defined above.

The recovery method includes, for example, the method described in J-A-62-198678, and the method of carrying out the hydrogenation in the range from 0 to 60aboutWith under normal pressure or under pressure in an organic solvent (e.g. ethanol, ethyl acetate) using a catalyst such as platinum dioxide, palladium-carbon, etc.

Some of the compounds having formula (15) is known from JP-A-62-198678. Other compounds of formula (15) floor can be derived fluorinated benzo-1,4-dioxole or other

o-Nitroaniline of formula (14) obtained by hydrolysis of compounds of o-nitroanilide formula

Z

(16) where X and Z are defined above; R2lower alkyl.

The reaction temperature is usually in the range from room temperature to 100aboutWith or temperature of heating under reflux of the solvent, the reaction time from instant to 24 hours, the Reaction is usually conducted in the presence of base or acid. Specific examples of the base are inorganic bases such as sodium hydroxide, potassium hydroxide, etc., Specific examples of the acid are inorganic acids such as hydrochloric acid, sulfuric acid and others. With regard to the amount of reagent used for the reaction, the amount of base or acid is from a catalytic amount to a large excess per mole of o-nitroanilide formula (16). The reaction is carried out with a solvent or without it, depending on the type of base or acid. Specific examples of solvents are aliphatic hydrocarbons (e.g. hexane, petroleum ether), aromatic hydrocarbons (e.g. benzene, toluene), halogenated hydrocarbons (e.g. chloroform, dihl the silts (for example, acetonitrile, isobutyronitrile), amides (for example, formamide, N,N-dimethylformamide), sulfur compounds (e.g., dimethylsulfoxide), alcohols (Napier, methanol, ethanol, 2-propanol), organic acids (e.g. formic acid, acetic acid, propionic acid), water, and mixtures thereof.

on-Nitroaniline compound of formula (14), where X is chlorine or bromine, can also be obtained by chlorination or bromirovanii compounds having the formula

Z

(17) where Z above.

In this reaction, the reaction temperature is usually in the range of 0aboutWith up to the temperature of heating under reflux of the solvent, and the reaction time is usually in the range from now until 24 hours regarding the number of reagents used for the reaction, the number glorieuses or brainwashes agent from 1 mol to a large excess per mole of the compounds having the formula (17).

As glorieuses agent you can use chlorine, N-chlorosuccinimide, sulfurylchloride. As brainwashes agent can be used bromine, N-bromosuccinimide, etc.,

Specific examples of the solvent used for this reaction, can be halogenated hydrocarbons (e.g. chloroform, four of the items (for example, formic, acetic, propionic acid), water, and mixtures thereof.

On-Nitroanilide the compound has the formula

< / BR>
(18)

where X, Z and R2above.

In this reaction, the reaction temperature usually ranges from -40about20aboutC, and the reaction time is usually in the range from now until 24 hours as nitriloside agent you can use fuming nitric acid, nitric acid, sodium nitrate and potassium nitrate. As a solvent it is possible to use acetic acid, acetic anhydride, sulfuric acid, fuming sulfuric acid, water and mixtures thereof. With regard to the amount of reagent used for the reaction, the number nitriloside agent from 1 mol to a large excess per mole of the compound represented by foruli (18).

Among the on-nitroaniline compounds of the formula (16) compounds of the formula

< / BR>
(19)

where R2lower alkyl, can be obtained by cyclization of compounds having the formula

< / BR>
(20)

where Y is bromine or chlorine;

R2lower alkyl, in the presence of metallic copper.

The reaction temperature is normally maintained within 50aboutWith up to the temperature of heating under reflux of the solvent, and the reaction time is on the mol of compound of formula (19).

This reaction is conducted usually in a solvent. Specific examples of the used solvents are amides (for example, formamide, N, N-dimethylformamide), sulfur compounds (e.g., dimethyl sulfoxide and mixtures thereof. After completion of the reaction the reaction solution, for example, is filtered and then subjected to further treatments such as extraction of the filtrate with an organic solvent, washing with water, concentration, etc. of the Obtained product is optionally purified by such operations as chromatography, recrystallization, etc. So you can get the desired connection.

Aniline compound of the formula (17) can be obtained by acylation anilides the compounds of formula

Z

(21) where X and Z are defined above.

The reaction temperature is usually maintained in the range from room temperature to 120aboutWith or temperature of heating under reflux of the solvent and the reaction time from instant to 24 hours the reaction is usually conducted in the presence of base or acid. Specific examples of bases are tertiary amines (e.g. pyridine, triethylamine, N,N-dimethylamine, tributylamine, N-methylmorpholine), inorganic bases the acid content of inorganic fillers (for example, formic acid, acetic acid, propionic acid) and inorganic acids (e.g. sulfuric acid). The amount of base or acid used for the reaction is from a catalytic amount to a large excess per mole of aniline compounds with formula (21).

Specific examples Alliluyeva agent used in this reaction are the corresponding acid anhydrides, acid halide, ether compounds, carboxylic acids, etc. the Number Alliluyeva agent used for the reaction is from 1 mol to a large excess per mole of aniline compounds of formula (21).

Used solvent is determined depending on a base or acid. If a solvent is used, it includes aliphatic hydrocarbons (e.g. hexane, petroleum ether), aromatic hydrocarbons (e.g. benzene, toluene), halogenated hydrocarbons (e.g. chloroform, dichloroethane), ethers (for example, diethylether, dioxane, tetrahydrofuran), ketones (e.g. acetone, methyl ethyl ketone), NITRILES (e.g. acetonitrile, isobutyronitrile), amides (for example, formamide, N,N-dimethylformamide), sulfur compounds (e.g., dimetilan the P CLASS="ptx2">

Among the compounds with formula (18) compounds of the formula

< / BR>
(22) where R2lower alkyl group, are obtained by cyclization of the compounds of formula

< / BR>
(23) where Y1and Y2independently hydrogen, bromine or chlorine, provided that Y1and Y2are not simultaneously a hydrogen atom; R2lower alkyl, with metallic copper.

This cyclization reaction can be performed as well as the cyclization of the compounds of formula (20).

Aniline compound of the formula (21) is disclosed or may be obtained by methods described, for example, Liebigs Ann. Chem. 730, 16-30, 1969, and JP-A-55-69676, USP 4,767,779, Chemical Abstracts, 60,13352 etc.

Way other than described, nitroaniline compound of the formula (17) can also be obtained by reaction of compounds of formula

Z

(24) where Z is defined above; Y3nitro or halogen,

with ammonia.

In this reaction, the reaction temperature is maintained between 0aboutWith up to a temperature of solvent under reflux and the reaction time is usually in the range from instant to 24 hours

As for the amounts of reactants for the reaction amount of ammonia is from 1 mol to a large excess per mole of the compound with formula (23).

the odes (for example, hexane, petroleum ether), aromatic hydrocarbons (e.g. benzene, toluene), ethers (for example, diethylether, dioxane, tetrahydrofuran), amides (for example, formamide, N,N-dimethylformamide), sulfur compounds (e.g., dimethyl - sulfoxide), alcohols (e.g. methanol, ethanol, 2-propanol), water and mixtures thereof.

Some of the compounds of formula (23) is known from Chemical Abstracts, 60, s(1964) or JP-A-198678. Other compounds with formula (23) can be obtained in the same manner as in JP-A-62-198678, based on 1,2-diftormetilirovaniya or other connection.

This connection can be used as an active ingredient for agricultural and horticultural fungicides without adding any other components. It is usually molded into emulsifiable concentrates, wettable powders, suspensions, dusts, granules, dry flowable compositions, etc. by mixing with other solid carriers, liquid carriers, gaseous carriers, surface-active agents and other media. In this case, the contents of this connection, which is the active ingredient in the compositions is typically from 0.01 to 99%, preferably 0.1 to 80%

Specific examples of solid carriers are small under silicon, clay fubasami, bentonite, Terra Alba), only, other inorganic minerals (Napier, sericite, calcite powder, quartz powder, activated carbon, calcium carbonate, hydrogenated silicon), chemical fertilizers (e.g. ammonium sulfate, ammonium phosphate, ammonium nitrate, urea, ammonium chloride), silo, powder from a nutshell, etc.

Specific examples of liquid carriers are water, alcohols (e.g. methanol, ethanol, ethylene glycol, cellosolve), ketones (e.g. acetone, methyl ethyl ketone, isophorone), aromatic hydrocarbons (e.g. benzene, toluene, xylene, ethylbenzene, methylnaphthalene), aliphatic hydrocarbons (e.g. n-hexane, cyclohexane, kerosene, gas oil), esters (e.g. ethyl acetate, butyl acetate), NITRILES (for example, acetonitrile, isobutyronitrile), ethers (e.g. dioxane, diisopropyl ether), acid amides (e.g. dimethylformamide, dimethylacetamide), halogenated hydrocarbons (e.g. dichloroethane, trichloroethane, carbon tetrachloride), vegetable oils (e.g. soybean oil, cotton oil, dimethylsulfoxide, etc.

Specific examples of gaseous carriers, i.e., jet fuel, are freon, butane, dookies esters, the alkyl sulphonates, alkylarylsulphonates, diallylmalonate, salts of polyoxyethylene alkylsilanes ether phosphoric acid, naphthalene - acid, formaldehyde, condensates, etc., and nonionic surfactants, such as polyoxyethylene, ethers, polyoxyethylene polyoxypropylene block copolymers, esters, sorbitol fatty acid esters of polyhydric alcohols, sugar derivatives, alcohol, etc.

Specific examples of the fixing agents and dispersing agents include casein, gelatin, polysaccharides (e.g. starch powder, gum Arabic, cellulose derivatives), lignin derivatives (e.g., lignosulfonate, alginic acid, bentonite, synthetic water-soluble high polymers (e.g. polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylic acid), etc.

Specific examples of stabilizing agents include phosphate, isopropyl acid (FIC), 2,6-decret-butyl-4 - METHYLPHENOL, a mixture of 2-tert-butyl-4-methoxyphenol and 3-tert-butyl-4-methoxyphenol, vegetable oils, mineral oils, surfactants, fatty acids and their esters, etc.

Methods of application of the present compounds deciduous application, tillage, desinfecte seeds, etc. But can use the ingredient for agricultural and horticultural fungicides, the dosage of this ingredient varies depending on culture, diseases, degrees of disease outbreaks, type of drug, methods of application, number of applications, weather conditions, etc., Usual dosage is 0.01-50 g/acre, preferably 0.05 to 10 g/acre. If emulsifiable concentrates, wettable powders, suspensions, dry flowable concentrates, etc. are applied diluted with water, the concentration of application of the active ingredient is 0.0001 to 0.5%, preferably of 0.0005-0.2% of Dust, granules, etc. are used as the model without dilution.

Plant disease that can be controlled for in this connection, the following: downy mildew of vegetables and Japanese horseradish (Peronospora. brassicae), downy mildew of spinach (Peronospora. spinaciae), downy mildew of tobacco (Peronospora. tabacina), downy mildew of cucumber (Pseudoperonospora cubensis), downy mildew of grape (Plasmopara viticola), late blight of Apple, strawberry and Zhen-shenja (Phytophthora cactorum), fitoterapia rot of tomato and cucumber (Phytophthora capsici), late blight of pineapple (Phytophthora cinnamomi), late blight of potatoes, tomatoes and eggplant, (Phytophthora infestans)the late blight tobacco, beans and onions-Batuna (Phytophthora nicotianae), asphyxiation spinach (Pythium sp.), the cucumber damping off (Pythium aphanidermatum), vipranarayana can be used as agricultural and horticultural fungicides on the fields, groves, plantations, pastures, meadows, etc. It can also be used in mixtures with other agricultural and horticultural fungicides. In addition, it can be used in a mixture with other insecticides, acaricides, nematicides, herbicides, plant growth regulators and fertilizers.

The present invention provides excellent preventive and therapeutic effect especially in various diseases caused Phycomyetes. One or more of these compounds can be mixed with at least one fungicide-active ingredient selected from the group consisting of CHLOROTHALONIL, fluazinam, dichlofluanid, fosetyl-aluminum, circular imenik fungicides (for example, Captan, captafol, folpet), dithiocarbamate fungicides (e.g., MANEB, MANCOZEB, Tirana, sirama, propineb), inorganic or organic copper fungicide (for example, basic copper sulfate, basic copper chloride, copper hydroxide, oxine copper), cymoxanil, acylalanines fungicides (for example, metalaxyl, paralexia, oporoza, ciproterona, benalaxyl, oxadixyl) and compounds disclosed in JP-a-1-301681, for example N-[cyano (2'-furyl)methyl] -2,4 - dimethylthiazol-5-carboxamide, N-[cyano(2'-thienyl)methyl] -]-2,4-dimethylthiazol-5-carboxamid, N-[cyano (2'-furyl)methyl]-2-methyl-4-utiltity-5-carboxamide, N-[cyano(3'-furyl)methyl] -2-methyl-4-utiltity-5-carboxamide, N-[cyano(2'-thienyl)-methyl] -2-methyl-4-utilties - ol-5-carboxamide and N-[cyano(3'-thienyl)methyl] -2-methyl-4-utiltity-5 - carboxamide. The resulting mixture can be used as a fungicide in the same way for these compounds as described. Mixing ratio of these compounds with CHLOROTHALONIL, fluazinam, dichlofluanide, foretelling, cyclic imename fungicides, dithiocarbamate fungicides or inorganic or organic copper fungicide is in the range of 1:(1-200) weight of the active ingredient.

Mixing ratio of these compounds with cymoxanil, allaluminum fungicides or the compounds disclosed in JP-a-I-301681 is (1:(0.1 to 20) weight of the active ingredient. These active ingredients can be used by mixing them, and then by molding, as described above, or by molding each of them, as described above, and then mixing. The use of these compounds in a mixture with other fungicides provides a synergistic improvement in efficiency especially in various diseases caused by Phycomycetes.

The image is p R I m e R 1. 2.83 G of the compound 2-cyanobenzylidene [compound of the formula (2), where X IS N; Z IS F2CFHO; was dissolved in 50 ml of acetonitrile. To the solution was added 3.8 g of potassium carbonate. The resulting mixture was heated under reflux for 15 minutes then injected 2.6 g of dimethylsulfoxide. The reflux was continued for another 40 minutes the Reaction solution was poured into ice water and was extracted with ethyl acetate. The organic layer was washed with water and dried over anhydrous sodium sulfate. The residue was obtained by removing the solvent from the dried layer by distillation. Column chromatography of the residue on silica gel with toluene as the solvent for elution gave 1,53 g a derivative of benzimidazole [present compound 1] formula (1), where X Is N; Z-OCF2CFHO; R-CN; Q IS N(CH3)2.

P R I m m e R 2. 0.95 G of the present compound 1 was dissolved in 20 l of pyridine. The resulting solution was stirred 1 h and 45 min in the atmosphere of hydrogen sulfide. After the reaction, the reaction solution was extracted with ethyl acetate. The organic layer was washed with water and dried over anhydrous sodium sulfate. Crystals were obtained by removing the solvent from the dried layer by distillation. Column chromatography crystals on silica gel with ronidazole [present compound 4] formula (1), where X N; 2-F2CFHO, R-thiocarbamoyl; Q-N(CH3)2.

P R I m e R 3. 1.8 g of the compound 2-cyanobenzylidene [compound iii] of the formula (2), where X is Br; Z-OF2CFHO, was dissolved in 70 ml of acetonitrile. To the solution was added 1.5 g of potassium carbonate. The resulting mixture was heated under reflux for 20 minutes then it was added 1.2 g of dimethylsulfoxide. The reflux was continued for 1 h the Reaction solution was poured into ice water and was extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous sodium sulfate and concentrated. Column chromatography of the resulting residue on silica gel with chloroform as the solvent for elution and recrystallization him from hexane/ethyl acetate gave 1.18 g of the derivative of benzimidazole [present compound 3] of formula (1), where X Is Br; Z-OCF2CFHO; R-CN; Q IS N(CH3)2.

P R I m e R 4. 1.5 G of the compound 2-cyanobenzylidene [connection ii] formula (2), where X IS F; Z-F2CFHO, was dissolved in 50 ml of acetonitrile. To it was added 2.0 g of potassium carbonate. The resulting mixture was heated under reflux for 25 minutes After it was added 1.5 g of dimethylsulfoxide. The reflux predprinyali water, dried over anhydrous sodium sulfate and concentrated. Column chromatography of the resulting residue on silica gel with toluene as the solvent for elution and recrystallization from hexane/ethyl acetate gave 0.9 g of the derivative of benzimidazole [present compound 2] formula (1), where X Is F; Z-OCF2CFHO; R-SP; Q-N(CH3)2(the connection in the form of bubbles).

P R I m e R 5. 6.2 g of 2-cyanobenzylidene [compound iv] of the formula (2), where X H; Z-OCF2O, was dissolved in 100 ml of acetonitrile. To it was added 10 g of potassium carbonate. The resulting mixture was heated under reflux for 15 minutes then to it was added 6.7 g of dimethylsulfoxide. The reflux was continued for 15 minutes the Reaction solution was poured into ice water and was extracted with ethyl acetate. The organic layer was washed with water and dried over anhydrous sodium sulfate. Crystals were obtained by removing the solvent from the dried layer by distillation. Recrystallization of the crystals from hexane/ethyl acetate and then from chloroform/ methanol gave 2.4 g of the derivative of benzimidazole [this connection 15] formula (1), where X N; Z OCF2O; R-CN; Q N(CH3)2.

P R I m e R 6. 0.4 G of the present compound 15 was dissolved in 1 is delali between ethyl acetate and water. The organic layer was washed with water and dried over anhydrous sodium sulfate. Crystals were obtained by removing the solvent by distillation. Recrystallization of the crystals from hexane/ethyl acetate gave 0.24 g of the derivative of benzimidazole [this connection 18] formula (1), where X N; Z-F2On; R thiocarbamoyl; Q-N(CH3)2.

P R I m e R 7. 1.5 G of the compound 2-cyanobenzylidene [compound vi] formula (2), where X is Br; Z OCF2Oh, was dissolved in 60 ml of acetonitrile. To it was added 2.0 g of potassium carbonate. The resulting mixture was heated under reflux for 15 minutes then to it was added 2.9 g of dimethylsulfoxide. The reflux was continued for 15 minutes the Reaction solution was poured into ice water and was extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous sodium sulfate and concentrated. Column chromatography of the resulting residue on silica gel with chloroform as the solvent for elution and recrystallization from hexanediamine gave 1.3 g of the derivative of benzimidazole [this connection 17] formula (1), where X is Br; Z QCF2O; R CN; Q N(CH3)2.

Derived benzimidazole it was further recrystallized the GMO isomers and contains a group of SO2N(CH3)2attached to the nitrogen atom constituting the ring of the benzimidazole, most distant from bromine atom.

P R I m e R 8. 2,05 G of compound 2-cyanobenzylidene formula (II), where X (F; Z OCF2O, was dissolved in 50 ml of acetonitrile. To it was added 2.0 potassium carbonate. The resulting mixture was heated under reflux for 20 minutes then it was added 1.3 g of dimethylsulfoxide. The reflux was continued for 45 minutes the Reaction solution was poured into ice water and was extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous sodium sulfate and concentrated. Column chromatography of the resulting residue on silica gel with chloroform as the solvent for elution and recrystallization him from hexane/ethyl acetate gave 1,33 g a derivative of benzimidazole [this connection 16] of formula (1) where X (F; Z OCF2O; R-CN; Q N(CH3)2.

P R I m e R 9. 0.6 G of 2-cyanobenzylidene formula (2), where X N; Z CF2CF2O, was dissolved in 30 ml of acetonitrile. To it was added 0.75 g of potassium carbonate. The resulting mixture was heated under reflux for 20 minutes then it was added 0.4 g of dimethylsulfoxide. Heating acetate. The organic layer was washed with water and dried over anhydrous sodium sulfate. The residue was obtained by removing the solvent from the dried layer by distillation. Column chromatography of the residue on silica gel with toluene as the solvent for elution gave 0,23 g a derivative of benzimidazole [this connection 29] formula (1), where X N; Z-CF2CF2O; R-CN; Q IS N(CH3)2;

1H NMR spectrum showed that the product is a mixture of two Regio isomers.

Examples of this connection, which can be obtained in specified ways, shown in the table.1.

The following are examples for the connection of 2-cyanobenzylidene formula (2).

P R I m e R 10 (intermediate compound). 3.2 G of 2-(trichloromethyl)benzimidazole [connection 101] of the formula (11), where X N; Z F2CFHO, was dissolved in 30 ml of ethanol. The resulting solution was added dropwise to 4 ml of 25% aqueous ammonia at 5aboutC. After stirring for 1 h at 5-15aboutTo the reaction solution was poured into a mixture of ice/concentrated hydrochloric acid and was extracted with ethyl acetate. The organic layer was washed with water and dried over anhydrous sodium sulfate. Removal of the solvent from the h/SUB>CFHO.

P R I m e R 11 (intermediate compound). to 5.3 G of compound 2(trichloromethyl)benzimidazole [connection 104] of the formula (11), where X N; Z OCF2O, suspended in 100 ml of ethanol. The resulting solution was added dropwise to 40 ml of 25% aqueous ammonia at 5aboutC. After stirring for 1 h at 5aboutC (room temperature), the reaction solution was poured into a mixture of ice/concentrated hydrochloric acid and was extracted with ethyl acetate. The organic layer was washed with water and dried over anhydrous sodium sulfate. The removing solution of the dried layer by distillation gave 4.0 g of the compound 2-cyanobenzylidene [compound iv] of the formula (2), where X N; Z OCF2O.

P R I m e R 12 (intermediate compound). 1.0 G of compound 2-(trichloromethyl)benzimidazole[connection 107] of the formula (11), where X N; Z CF2CF2O, was dissolved in 20 g of ethanol. The resulting solution was added dropwise to 5 ml of 25% aqueous ammonia at 5aboutC. After stirring for 30 min in 5aboutTo the reaction solution was poured into a mixture of ice, concentrated hydrochloric acid and was extracted with ethyl acetate. The organic layer was washed with water and dried over anhydrous sodium sulfate. Removed the mules (2), where X N; Z CF2CF2O.

Examples of compounds which can be obtained in specified ways, shown in the table.2.

Further examples are used to obtain compounds 2-(trichloromethyl)benzimidazole with formula (11).

P R I m e p 13 (intermediate compound). 2.5 G of o-phenylenediamine [connection 201] formula (12), where X N; Z-OCF2CFHO, was dissolved in 50 ml of ethyl acetate. At room temperature, thereto was added 3.8 g of methyltrifluoroacetamide. The resulting mixture was stirred 1 h the Reaction solution was poured into ice water and the precipitated crystals were filtered off. The crystals were dissolved in ethyl acetate. The resulting solution was washed with water and dried over anhydrous sodium sulfate. The removing solution of the dried layer by distillation gave 3.2 g of the compound 2-(trichloromethyl)benzimidazole [connection 101] of the formula (11), where X N; Z OCF2CFHO.

P R I m e R 14 (intermediate compound). 8.6 G of the compound o-phenylenediamine [connection 204] formula (12), where X N; Z OCF2O, was dissolved in 80 ml of acetic acid. At room temperature was added 8.7 g of methyltrifluoroacetamide. The resulting mixture was stirred 20 minutes, the Reaction solution was poured into ice water and the precipitated crystals wodnym sodium sulfate. Removing the solvent from the dried layer by distillation gave 5.35 g of the compound 2-(trichloromethyl)benzimidazole [connection 104] of the formula (11), where X N; Z F2O.

P R I m e R 15 (intermediate compound). 1.0 G of the compound o-phenylenediamine [connection 207] formula (12), where X N; Z CF2CF2O, was dissolved in 20 ml of acetic acid. To the solution at room temperature was added 1.4 g of methyltrifluoroacetamide. The resulting mixture was stirred 12 h the Reaction solution was poured into ice water and the precipitated crystals were filtered off. The crystals were dissolved in ethyl acetate. The resulting solution was washed with water and dried over anhydrous sodium sulfate. Removing the solvent from the dried layer by distillation gave 1.0 g of the compound 2-(trichloromethyl)benzimidazole [connection 107] of the formula (11), where X N; Z CF2CF2O.

Examples of the compounds 2-(trichloromethyl)benzimidazole, which can be obtained as mentioned above, are given in table.3.

Further examples are used to obtain compounds of o-phenylenediamine with formula (12).

P R I m e R 16 (intermediate compound). 2.7 G of the compound o-nitroaniline [connection 302] of the formula (14), where X is Br; Z F2CF, was dissolved in a mixed of rastvorov iron in 3 ml of acetic acid and 30 ml of water at 40aboutC. After stirring at 50-60about20 min the reaction mixture was filtered through Celite. The filtrate was extracted with ethyl acetate. The organic layer was washed with an aqueous solution of sodium bicarbonate and then with water and dried over anhydrous sodium sulfate. Removing the solvent from the dried layer by distillation gave 2,44 g of compound o-phenylenediamine [connection 203] with formula (12), where X is Br; Z OCF2CFHO.

P R I m e R 17 (intermediate compound). 2,98 G of compound o-nitroaniline [connection 305] of the formula (14), where X is Br; Z OCF2Oh, was dissolved in a mixed solvent of 10 ml of ethyl acetate and 10 ml of acetic acid. The resulting solution was added dropwise at 40aboutTo a suspension of 2.4 g of iron powders in 2 ml of acetic acid and 20 ml of water. After stirring at 40-55about30 min the reaction mixture was filtered through Celite. The filtrate was extracted with ethyl acetate. The organic layer was washed with an aqueous solution of sodium bicarbonate and then with water and dried over anhydrous sodium sulfate. Removing the solvent from the dried layer by distillation gave 2,52 g of compound o-phenylenediamine [connection 206] with formula (12), where X is Br; Z F2O.

P R I m e R 18 (intermediate l of ethyl acetate and 15 ml of acetic acid. The resulting solution was added dropwise at 50aboutTo a suspension of 1 g of iron powders in 2 ml of acetic acid and 30 ml of water. After stirring at 50-60about10 min the reaction mixture was filtered through Celite. The filtrate was extracted with ethyl acetate. The organic layer was washed with an aqueous solution of sodium bicarbonate and then with water and dried over anhydrous sodium sulfate. Removing the solvent from the dried layer by distillation gave 1.0 g of the compound o-phenylenediamine [connection 207] formula (12), where X N; Z-CF2CF2O.

Connection o-phenylenediamine, which can be obtained in specified ways, shown in the table.4.

Further examples are used to obtain compounds of o-nitroaniline of formula (14).

P R I m e R 19 (intermediate compound). The mixture 5,07 g o-nitroanilide [connection 401] of the formula (16), where X N; Z OCF2CFH; R2CH310 ml of concentrated hydrochloric acid and 100 ml of methanol was heated under reflux 1 h of Reaction - ment solution was concentrated, poured into ice-cold water and podslushivaet potassium carbonate. After extraction with ethyl acetate the organic layer was washed with water and dried over anhydrous sodium sulfate. Removal of solvent from the p R I m e R 20 (intermediate compound). 2.67 g of compound 301 was dissolved in 30 ml of acetic acid. To the resulting solution was added dropwise 03, ml of bromine at room temperature. After the addition stirring is continued for 3 h at room temperature. The reaction solution was poured into ice water and the precipitated crystals were filtered off. The crystals were dissolved in ethyl acetate. The resulting solution was washed with water and dried over anhydrous sodium sulfate. Removing the solvent from the dried layer by distillation gave 2.7 g of the compound o-nitroaniline [connection 302] of the formula (14), where X is Br, Z OCF2CFHO.

P R I m e R 21 (intermediate compound).

A mixture of 7.69 g of o-nitroanilide [connection 402] of the formula (16), where X N, Z F2O; and R2CH310 ml of concentrated hydrochloric acid and 90 ml of methanol was heated under reflux for 1.5 hours, the Reaction solution was concentrated, poured into ice-cold water and podslushivaet potassium carbonate. After extraction with ethyl acetate the organic layer was washed with water and dried over anhydrous sodium sulfate. Removing the solvent from the dried layer by distillation gave the 4.65 g of compound 303 of the formula (14), where X N, Z OCF2O.

P R I m e R 22 (intermediate compound). and room temperature. Once added, the stirring continued for 2.5 h at room temperature (40aboutC). The reaction solution was poured into ice water and the precipitated crystals were filtered off. The crystals were dissolved in ethyl acetate. The resulting solution was washed with water and dried over anhydrous sodium sulfate. Removing the solvent from the dried layer by distillation gave 2.50 g of the compound o-nitroaniline [connection 305] of the formula (14), where X is Br; Z OCF2O.

P R I m e R 23 (intermediate compound). A mixture of 1.32 g of o-nitroanilide formula

(26)

5 ml of concentrated hydrochloric acid and 50 ml of methanol was heated under reflux for 80 minutes, the Reaction solution was concentrated, poured into ice-cold water and podslushivaet potassium carbonate. After extraction with ethyl acetate the organic layer was washed with water and dried over anhydrous sodium sulfate. Removing the solvent from the dried layer by distillation gave 1.1 g of o-nitroanilide [connection 306] of the formula (24).

P R I m e R 24 (intermediate compound). 200 G of compound o-nitro formula (15), where X H; Z OCF2O, were dissolved in 900 ml of N,N-dimethylformamide. The resulting solution was reacted at 70aboutWith 3.5 hours with simultaneous blowing it Ammianus Celite. The filtrate was extracted with titilate - rum. The organic layer was washed with water and dried over anhydrous sodium sulfate. Removing the solvent from the dried layer by distillation gave the rest. The residue was subjected to column chromatography on silica gel using chloroform as a solvent for elution to get to 112.4 g of o-nitroaniline [connection 303] of the formula (14), where X N; Z OCF2O.

P R I m e R 25 (intermediate compound). to 1.60 G of compound o-chloronota formula

< / BR>
(27) was dissolved in 30 ml of N,N-dimethylformamide. The resulting solution was reacted at 90aboutC for 1 h with the injection of ammonia. After that, the reaction solution was poured into ice water and was extracted with ethyl acetate. The organic layer was washed with water. The washed layer was dried over anhydrous sodium sulfate. Removing the solvent from the dried layer by distillation gave the rest. The residue was subjected to column chromatography on silica gel using dichloromethane as a solvent for elution to obtain 0.9 g of o-nitroaniline [join 308] of the formula (14) where X N; Z CF2OCF2.

Compounds that can be obtained as mentioned above, are given in table. 5.2CFHO; R2CH3was added to 50 ml of concentrated sulfuric acid at -15aboutC. After the addition the stirring was continued for 2 h at (-15) (-10)aboutC. the Reaction solution was poured into ice water and the precipitated crystals were filtered off. The crystals were dissolved in ethyl acetate. The resulting solution was washed with water and dried over anhydrous sodium sulfate. The residue was obtained by removing the solvent from the dried layer by distillation. Column chromatography of the residue on silica gel with chloroform gave 5.0 g of o-nitroanilide [connection 401] of the formula (16), where X N; Z OCF2CFHO and R2CH3.

P R I m e R 27. 8,9 G anilide [connection 502] formula (18), where X N; Z OCF2O; R2CH3added to 80 ml of concentrated sulfuric acid. To the mixture was added dropwise a mixture of 7.5 ml of fuming nitric acid and 15 ml of concentrated sulfuric acid at 0aboutC. After the addition the stirring was continued for 0.5 h at (-10)-0aboutC. the Reaction solution was poured into ice water and the precipitated crystals were filtered off. The crystals were dissolved in ethyl acetate. The resulting solution was washed with water and dried over anhydrous sodium sulfate. The residue was obtained by removing the RAM gave of 7.69 g of o-nitroanilide [connection 402] of the formula (16), where X N; Z OCF2ON; R2CH3.

P R I m e R 28. 2,69 g anilide connection formulas

< / BR>
(28) was added to a mixture of 2.5 ml of fuming nitric acid and 5 ml of concentrated sulfuric acid at -10aboutC. After the addition the stirring was continued for 1 h at (-10)-0aboutC. the Reaction solution was poured into ice water and the precipitated crystals were filtered off. The crystals were dissolved in ethyl acetate. The resulting solution was washed with water and dried over anhydrous sodium sulfate. The residue was obtained by removing the solvent from the dried layer by distillation. Column chromatography of the residue on silica gel with chloroform as the solvent for elution gave 1,32 g o-nitroacetanilide [connection 404] formula (26).

P R I m e R 29. 7,80 G of compound of formula (20), where Y is Cl; R2CH3, was dissolved in 70 ml of N,N-dimethylformamide. To the solution was added 8.0 g of copper powder and 0.5 g of 2,2'-bipyridyl. After that, stirring was continued at 140about2 hours After completion of the reaction, the reaction solution was filtered through Celite. The filtrate was extracted with titilation. The organic layer was washed with water and dried over anhydrous sodium sulfate. The residue was obtained by removing the solvent from wissende elution and recrystallization him from hexane/ethyl acetate gave a 3.06 g of o-nitroanilide [connection 404] formula (26).

Compounds obtained by the above methods, are given in table.6.

Further examples will be provided on receipt of a connection anilide formula (18).

P R I m e R 30. 4.8 G of aniline compounds of formula (21), where X N; Z OCF2CFHO, was dissolved in 50 ml of acetic acid and 2.4 ml of acetic anhydride. The resulting solution was stirred at 70aboutWith 10 minutes the Reaction solution was poured into ice water and was extracted with ethyl acetate. The organic layer was washed with water and dried over anhydrous sodium sulfate. Distillation was obtained residue (removal of solvent from the dried layer). Column chromatography of the residue on silica gel with chloroform and ethyl acetate as eluent gave or 4.31 g anilides connection [connection 501] formula (18), where X N; Z F2FHO; R2CH3.

P R I m e R 31. of 8.4 G of aniline compounds of formula (21), where X N; Z OCF2O, was dissolved in 100 ml of acetic acid and 5 ml of acetic anhydride. The resulting solution was stirred at 60aboutWith 5 minutes the Reaction solution was poured into ice water and was extracted with ethyl acetate. The organic layer was washed with water and dried over anhydrous sodium sulfate. The residue was obtained by removing the solvent from the dried NTA gave 8,93 g anilides connection [connection 502] formula (18), where X N; Z F2O; R2-CH3.

Aniline compounds obtained are described methods, are presented in table.7.

Further examples of the preparation of the compositions. In the examples, parts are given by weight.

P R I m e R 32. Careful grinding into powder and mixing 50 h of each of compounds 1 78, 3 h of calcium lignosulfonate, 2 h lauryl sodium and 45 p.m. synthetic hydrogenated silicon dioxide gives obtain wettable powder of each of these compounds.

P R I m e R 33. Mix 25 h of each of compounds 1 78, 3 p.m sorbitanoleat of polyoxyethylene, 3 hours of CMC and 69 h of water. Wet grinding the mixture until the particle size of the active ingredient 5 μm or less gives the receipt suspension of each of these compounds.

P R I m e R 34. Careful grinding into powder and mixing 2 h of each of compounds 1 78, 88 including kaolin clay and 10 o'clock talc get the dust of each of these compounds.

P R I m e R 35. Thorough mixing 20 hours each of compounds 1 78, 14 hours polyoxyethylenesorbitan ether, 6 hours of dodecylbenzenesulfonate calcium and 60 hours of xylene get emulsion concentrate of each of these compounds.

P R I m e the tion, 30 hours of bentonite and 65 hours of kaolin clay are well pulverized and mixed. The resulting mixture was well mixed with water, granulated and dried to obtain pellets of each of these compounds.

Next, using the experimental examples show the usefulness of the present compounds as an agricultural and horticultural fungicide. As control was used MANCOZEB (wettable powder) as picometer-controlling agent. Regulatory activity in experimental examples 37-40 were evaluated in six stages (5,4,3,2,1,0) control indicator microscopic observation of the condition of the disease of the tested plants, i.e., the number of colonies and infection on leaves, stems and so on during the inspection.

5. The infected area is not observed at all.

4. The size of the infected area of less than 10% compared with the untreated experimental plot.

3. The size of the infected area of less than 30% in comparison with untreated experimental plot.

2. The size of the infected area of less than 50% compared with untreated experimental plot.

1. The size of the infected area of less than 75% compared to untreated experimental plot.

0. The size of the infested areas experience on late blight of tomatoes Phytophora infestans (preventive action).

Plastic pots were filled with spescom, planted tomatoes and cultured for 20 days in a greenhouse to obtain shoots with 2-3 true leaves. After that, wettable powder, experienced connection, prepared in accordance with example 32, was diluted with water to the desired concentration was sprayed on the foliage sprouts, so that the liquid completely covers the surface of the foliage. After spraying, the sprouts were inoculable by spraying a suspension of spores of Phytophtora infestans. After inoculation sprouts kept at 20aboutWith high humidity during the day and then were cultured for 7 Nam in the light. Then examined the regulatory activity.

The results are shown in table.8.

P R I m e R 38. Control experience on late blight of tomato Phytophthora infestans (therapeutic effect). Plastic pots were filled with spescom, planted tomatoes and cultured for 20 days in a greenhouse to obtain shoots with 2-3 true leaves. The sprouts were inoculable spray suspension support Phytophthora infestans. After inoculation sprouts kept at 20aboutWith high humidity day. Then wettable powder of the test compound prepared according to example 37, was diluted with water to the desired concentration and sprayed nwali 7 days. on the light. Then examined the regulatory activity. The results are given in table.9.

P R I m e R 39. Control experience on downy mildew of grapes Plasmopara viticola (preventive action). Plastic pots were filled with spescom, planted grapes and cultivated 50 days in the greenhouse to obtain shoots with 2-3 true leaves. After this wettable powder of the test compound prepared according to example 37, was diluted with water to the desired concentration was sprayed on the foliage sprouts, so that the liquid completely covers the surface of the foliage. After spraying, the sprouts were inoculable spraying a suspension of spores of Plasmopara viticola. After inoculation sprouts kept at 20aboutand high humidity during the day and then were cultured for 7 days in the light. Then examined the regulatory activity. The results are shown in table.10.

P R I m e R 40. Control experience on downy mildew of grapes Plasmopara viticola (therapeutic effect).

Plastic pots were filled with spescom, planted grapes and cultivated 50 days in the greenhouse to obtain shoots with 3-4 true leaves. The sprouts were inoculable spraying a suspension of spores of Plasmopara viticola. After inoculation radiatively in example 38, was diluted with water to the desired concentration was sprayed on the foliage sprouts, so that the liquid completely covers the surface of the foliage. After spraying, the shoots were cultured 7 days in the light. Then examined the regulatory activity. The results are shown in table.11.

P R I m e R 41. Control experience on late blight of tomato Phytophthora infestans (preventive action; the result of mixing with different fungicides).

Plastic pots were filled with spescom. They planted tomatoes (Ponterosa) and cultured for 30 days. in the greenhouse to obtain sprouts with 4-5 true leaves.

Wettable powders with the contents of one of these compounds, prepared in accordance with examples 32, various types of commercially available fungicides and one of these compounds and one of the fungicides was diluted with water to the desired concentration. After that, they were sprayed on the foliage sprouts, so that the liquid completely covers the surface of the foliage. After spraying, the shoots were placed for 6 days in a greenhouse. Then they were inoculable spraying a suspension of spores of Phytophthora infestans. After inoculation sprouts kept at 20aboutWith high humidity day and further cultured for 6 days in the light. For the lower h is of the equation, below.

Once the extent of the disease treated and untreated shoots was calculated disease control by the following equation. In table.12 gives the result.

The prevalence of the disease 5 disease Outbreak in 90% or more on

true sheets

The prevalence of the disease 4 disease Outbreak is not less than 90%

square true leaves

The prevalence of the disease 3 disease Outbreak at least 60%

square sheets

The prevalence of the disease 2 disease Outbreak at less than 30%

square sheets

The prevalence of the disease 1 disease Outbreak in less than 10%

square sheets

The prevalence of the disease 0.5 Outbreak in less than 5% of the area

sheets.

The prevalence of the disease 0 Outbreak is not observed

The degree of disease (%) 100

Disease control (%) 100

P R I m e R 42. Control experience on downy mildew of cucumbers Pseudoperonospora cubensis curative and preventive action; the result of mixing with different fungicides.

Plastic pots were filled with spescom. They were planted cucumber (variety Sagamihanjiro) and cultured for 30 days in a greenhouse to obtain sprouts with 4 true leaf. Then shoots the P>With high humidity day. Wettable powders with the contents of one of these compounds, prepared in accordance with example 32, various types of commercially available fungicides and mixtures of any of these compounds and one of the available fungicides was diluted with water to the desired concentration. After that, they were sprayed on the foliage sprouts, so that the liquid covers the surface of leaves. After spraying, the shoots were placed in 6 days. in the greenhouse. Then they were inoculable again by spraying a suspension of spores of Pseudoperonospora cubensis. After re-inoculation of shoots kept at 20aboutWith high humidity day and further cultured for 7 days in the light. For the bottom 2, 3 and 4 true leaves rates of disease was determined by the infected areas. Then the degree of the disease was determined by the following equation 4. In table.13 shows the results.

The prevalence of the disease 10 the Outbreak of 90% or more

true leaves

The prevalence of the disease 9 disease Outbreak less than 90%

square sheets

The prevalence of the disease 8 disease Outbreak less than 80%

square sheets

The prevalence of the disease 7 disease Outbreak less than 70%

square sheets

P is spiska disease less than

50% of the area of the sheets

The prevalence of the disease 4 disease Outbreak less than 40%

square sheets

The prevalence of the disease 3 disease Outbreak less than 30%

square sheets

The prevalence of the disease 2 disease Outbreak less than 20%

square sheets

The prevalence of the disease 1 disease Outbreak less than 10%

square sheets

The prevalence of the disease 0.5 Outbreak less than 5%

square sheets

The prevalence of the disease 0 Outbreak is not observed

The degree of disease (%) 100

Disease control (%) 100

The proposed connection has an excellent controlling effect on various plant diseases, especially diseases caused by Phycomycetes, takimi as downy mildew, late blight and other, and gives no phytotoxicity, which is a problem. Therefore, this connection is suitable for various applications as an active ingredient fungicides for agricultural and horticultural use.

1. A derivative of benzimidazole of General formula

< / BR>
where R is cyano or thiocarbamoyl;

Q is lower alkyl or a group represented by the formula NQ1Q2where Q1and QSTE taken with the nitrogen atom form a five-membered or six-membered nitrogen-containing ring, which may optionally include an oxygen atom;

X is hydrogen or halogen;

The Z group of the formula

(O)n(CF2)m(O)p(CY2)qOs,

where n,p,s=0 or 1, have the same or different values, m=1 or 2, q=0 or 1, provided that when q=0, p and s is not equal to 1 simultaneously, and Z together with two adjacent carbon atoms of the benzene ring forms a five-membered and six-membered cycle;

Y are the same or different, H,F,Cl, provided that CY2not a CCl2.

2. A derivative of benzimidazole of General formula

< / BR>
where X is hydrogen or halogen;

The Z group of the formula

(O)n(CF2)m(O)p(CY2)q(O)S,

where n, p,s0 or 1, have the same or different values, m is 1 or 2, q is 0 or 1, provided that when q is 0, both p and s is not equal to 1 simultaneously, and Z together with two adjacent carbon atoms of the benzene ring form a five-membered or six-membered cycle;

Y are the same or different, H,F,Cl, provided that CY2not a CCl2;

B CN or CCl3.

3.The compound of General formula

< / BR>
where X1halogen;

A group of NO2or NH2.

4. The connection formulas

< / BR>
where A GRU is SS="ptx2">

Priority signs:

03.06.91 when Q NQ1Q2where Q1=Q2is methyl, X is hydrogen,halogen,

< / BR>
05.06.91 when X is hydrogen, Q NQ1Q2where Q1=Q2- CH3,

< / BR>
24.07.91 when X is hydrogen, halogen, Q NQ1Q2where Q1Q2CH3,

< / BR>
where Z is selected from the group of CF2CFH, CF2CFCl, CF2CF2or CF2CH2;

26.02.92 when Q is lower alkyl or a group of the formula NQ1Q2where Q1and Q2independently lower alkyl, lower alkyl substituted by phenyl, or lower quinil, or Q1and Q2together with the nitrogen atom, form a five-membered or six-membered nitrogen-containing ring, which may optionally include oxygen, X is hydrogen, halogen, Z is the remaining values specified in the formula.

 

Same patents:

FIELD: herbicides, agriculture.

SUBSTANCE: invention describes a herbicide composition comprising components in the following their contents, g/l: phenmedifam, 30-160; desmedifam, 30-160; mixture of non-ionogenic and anion-active surface-active substance, 150-350; liquid carboxylic acid amide, 20-200; co-solvent, 30-300; citric acid, 2-6; 1-phenyl-(1,2,4-triazole-4-yl)urea, 2-20; solvent, the balance, up to 1 l. The composition can comprise additionally ethofumezat in the amount 30 g/l. Invention provides the development of herbicide composition based on phenmedifam and desmedifam possessing the enhanced herbicide activity that allows reducing doses of preparations in their consumptions.

EFFECT: improved herbicide activity of composition.

2 cl, 2 tbl, 1 ex

FIELD: organic chemistry.

SUBSTANCE: invention describes C2-phenyl-substituted cyclic ketoenols of the general formula: wherein W means hydrogen atom, alkyl with 1-6 carbon atoms; X means alkyl with 1-6 carbon atoms, alkenyl with 2-6 carbon atoms; Y means hydrogen atom, methyl, ethyl, isopropyl, alkenyl with 2-6 carbon atoms, ethynyl; Z means hydrogen atom, alkyl with 1-6 carbon atoms under condition that at least one of residues W, X, Y or Z means a chain with at least 2 carbon atoms but only one of residues X and Y can mean alkenyl with 2-6 carbon atoms; CKE means one of the following groups: , , and wherein A means hydrogen atom, alkyl with 1-6 carbon atoms; B means hydrogen atom, alkyl with 1-6 carbon atoms; A and B in common with carbon atom to which they are bound mean cycloalkyl with 5-6 carbon atoms wherein the ring carbon atom can be substituted with oxygen atom and can be substituted with alkyl with 1-6 carbon atoms or alkoxyl with 1-6 carbon atoms; A and B in common mean group of the formula: D means hydrogen atom or phenyl substituted with fluorine atom if CKE means group of the formula (4); G means hydrogen atom (a) or one of groups of the formula: or wherein R1 means alkyl with 1-6 carbon atoms, alkoxymethyl with 1-2 carbon atoms; R2 means alkyl with 1-4 carbon atoms; A and Q1 in common mean alkanediyl with 3-4 carbon atoms; Q2 means hydrogen atom. Invention provides preparing compound of the formula (I) possessing with insecticide, acaricide and herbicide activity.

EFFECT: valuable properties of compounds.

2 cl, 8 tbl, 32 ex

FIELD: chemistry.

SUBSTANCE: described are 2,4,6-phenyl-substituted cyclic ketoenols of formula (I, in which W, X, Y and CKE are given in invention formula. Also described are esters of acylamino acids of formula (II), substituted derivatives of phenylacetic acid of formula (XXIX), (XXVII), (XXXI), which are intermediate compounds for obtaining formula (I) compound.

EFFECT: obtaining herbicidal preparation containing combinations of biologically active substances, including (a), formula (I) compound and (b') improving compatibility with cultural plants mefenpyr-diethyl, with weight ratio 5-1:1-7.7.

9 cl, 46 tbl, 36 ex

FIELD: chemistry.

SUBSTANCE: compounds of formula (1) are described, where substitutes are as defined in the formula of invention. Methods of obtaining formula (1) compounds are described, when n equals 0. Described also is a fungicide composition based on formula (1) compounds and a phytopathogenic fungus control method which uses compounds in paragraph 1 or a composition based on the said compounds.

EFFECT: obtaining compounds with fungicide properties.

17 cl, 60 tbl, 5 ex

FIELD: chemistry.

SUBSTANCE: invention describes compounds of formula (1) , where substitutes are as defined in paragraph 1 of the invention. The compounds have fungicide properties. The method of obtaining formula (1) compounds is described, in which n equals 0. Described also is a fungicide composition based on formula (1) compounds and a phytopathogenic fungus control method which uses compounds in paragraph 1 or a composition based on the said compounds.

EFFECT: obtaining novel compounds which can be used as fungicides.

24 cl, 312 tbl, 14 ex

FIELD: chemistry.

SUBSTANCE: composition contains a) strigolactone derivative that was chosen from the list including

and (b) insecticidal compound that was chosen from the list including abamectin, aldicarb, beta-cyflutrin, chlorpyriphos-E, clothianidin, cyromazine, deltamethrin, вшадгиутягкщтб emamectin benzoate, fipronil, gamma-cygalogentrin, hexaflumuron, imidacloprid, L-cygalogentrin, methiocarb, pymetrozine, rinaksapir, spinosad, spirodiclofen, spiromesifen, spirotetramat, tebufenozide, tebufenpyrad, tefluthrin, tiamethoksam and thiodicarb with the mass ratio (a)/(b) from 1/1 to 1/1013. The efficient and nonphytotoxical amount of the composition is used by applying it to the seeds, leaves, stem, watering/dropwise application (chemization) on the seeds, plants ok plant fruit, or by putting it into the soil or nonreactive substrate, pumice stone, pyroclastic material/hassock, synthetic organic loadings, organic loadings or fluid substrate where the plant is growing or where it is going to grow.

EFFECT: increase in the efficiency of insect control.

11 cl

FIELD: chemistry.

SUBSTANCE: invention relates to agriculture. The composition for curative and preventive control of plant pathogenic fungi culture contains: a) a strigolactone derivative of formula (I), selected from a group comprising

, and b) a fungicidal compound selected from a group comprising N-[2-(1,3-dimethylbutyl)phenyl]-5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide, benalaxyl, ethyrimol, hymexazol, mefenoxam, metalaxyl, metalaxyl-M, benomyl, carbendazim, pencycuron, thiabendazole, zoxamide, boscalid, carboxin, flutolanil, furametpyr, penthiopyrad, thifluzamide, azoxystrobin, cyazofamid, dimoxystrobin, famoxadone, fenamidone, fluoxastrobin, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin, trifloxystrobin, fluazinam, silthiofam, cyprodinil, kasugamycin, mepanipyrim, pyrimethanil, fenpiclonil, fludioxonil, iprodione, procymidone, propamocarb, tolclofos-methyl, bitertanol, cyproconazole, difenoconazole, epoxiconazole, etaconazole, fenhexamid, fluquinconazole, flurprimidol, flutriafol, hexaconazole, imazalil, imibenconazole, ipconazole, metconazole, propiconazole, prothioconazole, simeconazole, spiroxamine, tebuconazole, tetraconazole, triadimefon, triadimenol, triflumizole, triticonazole, carpropamid, tolylfluanid, fluopicolide, isotianil, N-{2-[1,1'-bi(cyclopropyl)-2-yl]phenyl}-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide, propamocarb fosetylate, triazoxide, N-(3',4'-dichloro-5-fluorobiphenyl-2-yl)-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide, N-{2-[3-chloro-5-(trifluoromethyl)pyridin-2-yl]ethyl} -2-(trifluoromethyl)benzamide with weight ratio (a)/(b) ranging from 1/1 to 1/1014. An effective and non-phytotoxic amount of the composition is used via seed treatment, foliar application, stem application, drench/drip application (chemigation) to the seed, the plant or to the fruit of the plant, or to the soil and/or an inert substrate, pumice, pyroclastic materials/tuff, synthetic organic substrates, organic substrates or a liquid substrate, where the plant is grown or has to be grown.

EFFECT: invention increases activity of the composition.

3 cl

FIELD: chemistry.

SUBSTANCE: invention relates to agriculture. Agronomical composition includes (a) biocides and (b) products of alkoxylation of esters of di- or oligosaccharides.

EFFECT: invention makes it possible to increase composition stability.

11 cl, 4 tbl, 6 ex, 2 dwg

FIELD: chemistry.

SUBSTANCE: invention provides a method of encapsulating a preparation via a nonsolvent deposition method, characterised by that the core of the nanocapsules used is gibberellic acid, the envelope used is carrageenan, which is deposited from a suspension in benzene by adding tetrachloromethane as a nonsolvent, followed by drying at room temperature.

EFFECT: simpler and faster process of producing nanocapsules and reducing losses when producing nanocapsules.

3 ex

FIELD: agriculture.

SUBSTANCE: invention relates to agriculture. Plant growth stimulation is performed by treatment of plants with effective amount of compound according to formula: where any one of radicals R1, R2, R3, and R4 represents trifluoromethyl group, and others represent hydrogen atom, or salt of compound acceptable in agriculture.

EFFECT: invention allows improving treatment efficiency.

12 cl, 7 ex, 1 tbl

FIELD: agriculture.

SUBSTANCE: claimed composition contains (g/t): benzimidasole derivatives (e.g. agrocite, bendan, usgene, fundasol) as protectant not less than 300; and target additives: carbamide 20-25; potassium monosubstituted phosphate 9-12; potassium chloride 7-10; copper sulfate 120-125; zinc sulfate 120-125; magnesium sulfate 120-125; cobalt sulfate 10-12; manganese sulfate 15-17; ammonium molybdate 16-18; and water 1000-1050. Composition for seed pretreatment contains abovementioned components in the same ratio and water soluble film-forming agent in amount of 10-12 g/t.

EFFECT: decreased protectant consumption.

5 cl, 2 ex

FIELD: agriculture.

SUBSTANCE: the use of 2-methyl-4-dimethylaminomethyl-5-hydroxybenzoimidazole dihydrochloride as agent for enhancing of grain variety frost and winter resistance is disclosed.

EFFECT: increased winter crop resistance to foul weather conditions.

4 ex, 3 tbl, 2 dwg

FIELD: organic chemistry, antidotes, agriculture.

SUBSTANCE: invention describes using N-substituted 3-cyano-4,6-dimethyl-5-chloropyridyl-2-sulfonylamides of the formula (1-2): wherein in (1) R means benzimidozolyl-1; in (2) R means furfurylamino-group as antidotes of herbicide 2,4-dichlorophenoxyacetic acid in sunflower. Invention provides expanding assortment of biologically active substances prepared by synthetic method for their using in agriculture as antidotes against 2,4-D. Method involves treatment of sunflower seedlings damaged with herbicide by proposed N-substituted 3-cyano-4,6-dimethyl-5-chloropyridyl-2-sulfonylamides.

EFFECT: valuable biological properties of antidotes.

1 tbl, 3 ex

FIELD: agriculture.

SUBSTANCE: composition for seed pretreatment is described. It contains TMTD carbendasim, or tebuconazole and additionally it contains synergist, which is used as the quaternary ammonium salt in mass quantities 1-12%. The composition is presented in the form of concentrate suspension.

EFFECT: activity increase of existing substances in seeds pretreatment; reducing costs in pretreatment.

4 tbl, 2 ex

FIELD: chemistry.

SUBSTANCE: invention relates to [2-(azol-1-yl)alkylbenzimidazol-1-yl]alkanoic acids and their esters of general formula I, where Z and Y represent a nitrogen atom or a CH-group, or are simultaneously a C-CH=CH-CH=CH-C chain, together consisting of an annelated ring, n and m are equal or different and assume integer values from 1 to 3, R is a hydrogen atom or an alkyl group with 1 to 4 carbon atoms, except [2-(1H-benzimidazol-1-ylmethyl)-1H-benzimidazol-1-yl]acetic acid. The said compounds with general formula I are obtained through alkylation of 2-(azol-1-ylalkyl)benzimidazoles II with esters of ω-halogenalkanoic acids alkylacrylates and γ-butyrolacton in polar aprotonic and protonic solvents in the presence of carbonates of alkali metals, as well as when using interphase transfer catalysts. The invention also relates to a growth-regulating composition based on compounds of general formula I.

EFFECT: use of the derivative in the growth-regulating composition allows for achieving a growth retardant effect.

6 cl, 7 tbl, 9 ex

FIELD: medicine.

SUBSTANCE: there are described synergistic fungicidal combinations of biologically active substances which contain one carboxamide of general formula (I) , (group 1) where A, R1, R2 and R3 have values presented in the patent claim, and a biologically active substance chosen from compound groups specified in the patent claim (2) - (17) have. There is described application of said agent for undesired plant pathogenic fungi control.

EFFECT: extended range of the agents for undesired plant pathogenic fungi control.

8 cl, 13 tbl, 12 ex

FIELD: agriculture.

SUBSTANCE: invention relates to agriculture. Synergistic fungicidal combination of biologically active substances comprises a carboxamide of formula (I) where R1 is fluorine, R2 is chlorine, R3 is chlorine, R6 is methyl, R7 is difluoromethyl, R8 is hydrogen, and at least one biologically active substance selected from the group consisting of cyproconazole, metconazole, fenpropimorph and metrafenone. It is used for controlling unwanted phytopathogenic fungi.

EFFECT: invention enables to improve the efficiency of processing.

2 cl, 21 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to agriculture. Fungicidal preparation includes carbendazim in form of modification: salt of carbendazim with organic or mineral acid and auxiliary components with the following ratio, wt %: carbendazim salt with mineral or organic acid 20-65, surface-active substance 2-7.3, filler 0.5-5, film-former 0.3-2, hard water softener 0-1, antifreeze 0-20, dye 0-1, diluent - water the remaining part. As organic acid applied is alkylbenzolsulfoacid of formula C8-18H17-37C6H4SO3H or p-toluenesulfonic acid, and as mineral acid - hydrochloric or phosphoric, or boric acid.

EFFECT: invention makes it possible to reduce norms of active substance consumption with preservation of fungicidal activity.

3 cl, 20 ex, 3 tbl

FIELD: chemistry.

SUBSTANCE: rodenticide composition includes active substance - anticoagulant, gel-forming substance, stabiliser, dye and water. As anticoagulant composition contains tetrafenacine, as gel-forming substance it contains xanthane, or carrageenan, or mixture of xanthane and Carob gum, taken in weight ratio equal (1-9):(1-9), respectively, or mixture of carrageenan and Carob gum, taken in weight ratio, equal (1-9):(1-9), respectively, or mixture of xanthane and guar gum, taken in weight ratio, equal (1-9):(1-9). As stabiliser polyethylene glycol or triethylene glycol is used. Composition additionally contains sulfaquinoxaline with the following ratio of components, wt %: tetrafenacine 0.0025-0.05; sulfaquinoxaline 0.025-0.1; xanthane or carrageenan, Carob gum, or guar gum, or mixture of xanthane and Carob gum, taken in weight ratio, equal (1-9):(1-9), respectively, or mixture of carrageen and Carob gum, taken in weight ratio, equal (1-9):(1-9), respectively, or mixture of xanthane and guar gum, taken in weight ratio, equal (1-9):(1-9), respectively 0,3-15; dye 0.02-0.05; polyethylene glycol or triethylene glycol 3.0-20.0; water, or milk or milk whey - the remaining part.

EFFECT: invention makes it possible to use composition at temperatures below zero.

12 cl, 72 ex

FIELD: chemistry.

SUBSTANCE: invention relates to antifungal preparation, containing effective quantity of methyl ether of 2-benzimidazolylcarbamic acid, or its salts with inorganic and organic acids, or their hydrates, or its complex compounds with organometallic and inorganic salts, containing transition metal. Claimed invention demonstrates antifungal activity with respect to causative agents of mycoses from the group, including Trichophyton mentagrophytes var. Interdigitale, Trichophyton rubrum, Microsporum canis, Trichophyton mentagrophytes var. granulosum, Candida albicans. Antifungal activity has been detected with respect to pathogenic and opportunistic fungi, causing mycoses of mucosa and skin in humans and animals.

EFFECT: increased activity of preparation.

9 cl, 4 tbl, 28 ex

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