Derivatives chloropyridinyl and their acid additive salt and a means for combating phytopathogenic fungi

 

(57) Abstract:

The invention relates to new derivatives of chloropyridinyl formula I where Het is a group of formula a, b, C, d or e, R1is hydrogen, unsubstituted or substituted C1- C6alkyl, and the substituents selected from the group comprising halogen, phenyl, cyano, C1- C4alkoxy, C1- C4alkylthio,1- C4alkylsulphonyl; C2- C4alkenyl, unsubstituted or substituted C1- C4alkoxygroup; phenyl or unsubstituted or substituted 1 or 21- C4alkoxygroup, n = 1 or 2, and their acid additive salts. The compounds of formula I and their salts possess fungicidal activity and can be used in agriculture for combating phytopathogenic fungi. Also describes the means for combating phytopathogenic fungi. 2 S. and 2 C.p. f-crystals, 2 PL.

The invention relates to new nitrogen-containing heterocyclic compounds possessing biological activity, in particular derivatives chloropyridinyl and their acid additive salts and means for combating phytopathogenic fungi.

Known derivatives of pyrazole and elimidate, both regional and accepted application JP N Sho 51-7669, application DE N 1926206).

Object of the invention is the expansion of the range of nitrogen-containing heterocyclic compounds having fungicidal activity.

The problem is solved proposed derivatives chloropyridinyl formula (I)

< / BR>
where Het is a group of the formula

< / BR>
< / BR>
R1is hydrogen, unsubstituted or substituted alkyl with 1-6 carbon atoms, and substituents selected from the group comprising halogen, phenyl, cyano, alkoxy with 1 to 4 carbon atoms, alkylthio with 1 to 4 carbon atoms, alkylsulphonyl with 1-4 carbon atoms; alkoxycarbonyl with 1 to 4 carbon atoms, alkenyl with 2 to 4 carbon atoms, unsubstituted or substituted by alkoxycarbonyl with 1 to 4 carbon atoms; phenyl or unsubstituted or substituted 1 or 2 alkoxygroup with 1 to 4 carbon atoms, pyrimidinyl;

n is the number 1 or 2,

and their acid additive salts.

Preferred derivatives of chloropyridinyl formula (I) are compounds that have

Het is a group of the formula

< / BR>
< / BR>
n - 1; and a chlorine atom is linked to position 2 or 6 peredelnoj group, or

n is the number 2, and the chlorine atoms are associated with positions 2 and 3 peredelnoj group,

R1is hydrogen or alkyl with 1 the group including halogen, phenyl, cyano, alkoxy with 1 to 4 carbon atoms, alkylthio with 1 to 4 carbon atoms, alkylsulphonyl with 1 to 4 carbon atoms, alkoxycarbonyl with 1 to 4 carbon atoms;

or

R1alkenyl with 2 to 4 carbon atoms, unsubstituted or substituted by 1 to 3 same or different alkoxy with 1 to 4 carbon atoms;

or

R1is phenyl or pyrimidinyl, unsubstituted or substituted by 1 or 2 identical or different substituents selected from the group comprising methoxy, ethoxy.

In particular, preferred compounds of formula (I), where

Het is a group of the formula

< / BR>
< / BR>
n - 1, and a chlorine atom is linked to position 2 or 6 peredelnoj group, or

n is the number 2, and the chlorine atoms are associated with positions 2 and 6 peredelnoj group,

R1is hydrogen or alkyl with 1 to 4 carbon atoms, unsubstituted or substituted by 1 to 3 identical or different substituents selected from the group comprising fluorine, chlorine, phenyl, cyano, methoxy, methylthio, methylcarbamyl, tert.butylcarbamoyl, methoxycarbonyl, etoxycarbonyl,

or

R1alkenyl with 2 to 4 carbon atoms, unsubstituted or substituted by 1 to 3 methoxypropane,

or

R1is phenyl or pyrimidinyl, nezameshchenny the additive salts can be obtained by ways of peers, for example,

(a) by the interaction of globaldeleteatom formula (II)

< / BR>
where n has the above meaning, and

Hal means halogen,

with a heterocyclic compound of the formula (III)

Het-H (III)

where Het is a group of the formula

< / BR>
< / BR>
where R1has the above value

in the presence of an inert diluent and, if necessary, in the presence of an acid binding agent and, if necessary, in the presence of a catalyst, or

b) by reacting derivatives of chloropyridinyl formula (I')

< / BR>
where n has the above meaning, and

Het1group of the formula

< / BR>
< / BR>
with iodic acid or a salt of iodic acid in the presence dioxide osmium and inert diluent,

or

C) by reacting derivatives of chloropyridinyl formula (I")

< / BR>
where n has the above meaning, and

Het2group of the formula

< / BR>
< / BR>
with a halide compound of the formula

R2Hal (IV)

where Hal has the above value,

R2matter of the radical R1with the exception of hydrogen,

in the presence of an inert diluent and, if necessary, in the presence of binding free form or in the form of an acid additive salt.

For the salt formation is preferably used kaleidotrope acid, such as, for example, hydrochloric acid or Hydrobromic acid, in particular hydrochloric acid, phosphoric acid, nitric acid, sulfuric acid, mono - and bifunctional carboxylic acids and hydroxycarboxylic acids, such as, for example, acetic acid, maleic acid, succinic acid, fumaric acid, tartaric acid, citric acid, salicylic acid, sorbic acid and lactic acid, sulfonic acid, such as, for example, n - toluensulfonate acid, 1,5-naphthalenedisulfonic acid or camphorsulfonate, as well as saccharin and tishrin.

In the case of the use as starting compounds of the acid chloride 2,6-dichlorophenylamino acid and 1-methyl-1,2,4 - triazole (a) proceeds according to the following reaction scheme:

< / BR>
If the starting compound used is 5-(2',6'- dichloro-4'-pyridylcarbonyl)-1-ethynyl-1,2,4-triazole, and the oxidant - periodate sodium in the presence dioxide osmium, the method (b) proceeds by the following reaction scheme:

< / BR>
In the case of the use as starting compounds 2-(2',6'- dichloro-4'-pyridylcarbonyl)-imida the halides of the formula (II), heterocyclic compounds of the formula (III) and halide compounds of formula (IV) are known and can be obtained by known methods.

Derivatives chloropyridinyl formula (I') can be obtained by the aforementioned method (a), and derivatives of formula (I) can be obtained by the aforementioned method (b).

As diluents in carrying out process (a) can be applied to all conventional in such reactions inert organic solvents. Preferably use the following solvents: non-chlorinated or chlorinated aliphatic, alicyclic and aromatic hydrocarbons, such as, for example, pentane, hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene and dichlorobenzene; ethers, such as, for example, a simple diethyl ether, simple metaliteracy ether, simple diisopropyl ether, simple disutility ether, dioxane, dimethoxyethane, tetrahydrofuran and simple dimethylaminomethylene ether; ketones, such as, for example, acetone, methyl ethyl ketone, methylisobutylketone and methyl isobutyl ketone; NITRILES, such as, for example, acetonitrile and propionitrile; esters, such as, for example, the example, dimethylformamide, dimethylacetamide, N - organic, 1,3-dimethyl-2-imidazolidinone and hexamethylphosphorotriamide; sulfones and sulfoxidov, such as, for example, dimethyl sulfoxide and sulfolane; bases, such as pyridine, and nitromethane.

Method (a) can be performed in the presence of an acid binding agent and catalyst, if used heterocyclic compounds of the formula (III), where Het means imidazolidinyl, 1,2,4 - triazolyl, thiazolidine, benzothiazolyl or benzimidazolyl group. Suitable acid binding agents are organic bases, such as, for example, tertiary amines, dialkylaminoalkyl and pyridine, such as, for example, triethylamine, 1,1,4,4-tetramethylethylenediamine, N,N-dimethylaniline, N,N-diethylaniline, pyridine, 4-dimethylaminopyridine, 1,4-diazabicyclo[2,2,2] octane and 1,8-diazabicyclo[5,4,0] undec-6-ene. Examples of suitable catalysts are: Quaternary ammonium salt, such as, for example, bromide of Tetramethylammonium, bromide of tetrapropylammonium, tetrabutylammonium bromide, tetrabutylammonium bisulfate, tetrabutylammonium iodide, chloride of trioctylamine, bromide of benzyltriethylammonium, bromide, butylpyrazine, bromide, heptylamine and exil-18-crown-6, 18-crown-6, [2,2,2] -cryptit, [2,1,1] -cryptit, [2,2,1]-cryptit, [2,2,3]-cryptit, [3,2,2]-cryptit.

Method (a) can be performed in the presence of Lewis acid as a catalyst, if used heterocyclic compounds of the formula (III), in which Het denotes thienyl, follow or pyrrolidino group. Examples of suitable Lewis acids are:

aluminium chloride, patalita antimony, iron chloride (III) chloride tin (IV), titanium tetrachloride, zinc chloride, hydrogen fluoride, boron fluoride, phosphoric acid and polyphosphoric acid.

When carrying out process (a) the reaction temperature can be varied within wide limits. The reaction is usually carried out at a temperature from about -76oC to approximately +150oC, preferably from 0oC to about 120oC.

Method (a) is usually carried out at atmospheric pressure, however, the reaction may and at elevated or reduced pressure.

When carrying out process (a), generally 1 mol of globaldeleteatom formula (II) is subjected to interaction with 0.1 to 10 mol heterocyclic compounds of the formula (III), and the reaction is carried out in the presence of a diluent and, if necessary, in the presence of the este diluents when carrying out process (b) can be used in all conventional in such reactions inert organic solvents. Preferably use the following solvents: non-chlorinated or chlorinated aliphatic, alicyclic and aromatic hydrocarbons, such as, for example, pentane, hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene, xylene, dichloromethane, chlorobenzene and dichlorobenzene; ethers, such as, for example, a simple diethyl ether, simple metaliteracy ether, simple diisopropyl ether, simple disutility ether, dioxane, dimethoxyethane, tetrahydrofuran and simple dimethylaminomethylene ether; ketones, such as, for example, acetone, methyl ethyl ketone, methylisobutylketone and methyl isobutyl ketone; NITRILES, such as, for example, acetonitrile and propionitrile; alcohols, such as, for example, methanol, ethanol, isopropanol, butanol and ethylene glycol; esters, such as, for example, a complex ethyl ester of acetic acid and complex amyl ester of acetic acid; acid amides, such as, for example, dimethylformamide, dimethylacetamide, N-organic, 1,3-dimethyl-2-imidazolidinone and hexamethylphosphorotriamide; sulfones and sulfoxidov, such as, for example, dimethyl sulfoxide and sulfolane; and bases, for example pyridine. You can also use as a diluent mixture of water and sechiba (b) the reaction temperature can be varied within wide limits. The reaction is usually carried out at a temperature from about -70oC to approximately +150oC, preferably from 20oC to about 120oC.

Method (b) is usually carried out at atmospheric pressure, however, the reaction may and at elevated or reduced pressure.

When carrying out process (b), generally 1 mol of globaldeleteatom formula (I') is subjected to interaction with 2-20 mol iodic acid or its salts, and the reaction is carried out in the presence dioxide osmium and diluent. The product is processed by conventional methods.

As diluents in carrying out process (C) can be applied to all conventional in such reactions inert organic solvents. Preferably use the following solvents: non-chlorinated or chlorinated aliphatic, alicyclic and aromatic hydrocarbons, such as, for example, pentane, hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene and dichlorobenzene; ethers, such as, for example, a simple ethyl ester, simple metaliteracy ether, simple isopropyl ether, simple butyl ether, dioxane, dontrel and propionitrile; alcohols, such as, for example, methanol, ethanol, isopropanol, butanol and ethylene glycol; esters, such as, for example, a complex ethyl ester of acetic acid and complex amyl ester of acetic acid; acid amides, such as, for example, dimethylformamide, dimethylacetamide, N - organic, 1,3-dimethyl-2-imidazolidinone and hexamethylphosphorotriamide; sulfones and sulfoxidov, such as, for example, dimethyl sulfoxide and sulfolane: as well as the base, for example pyridine.

Suitable for carrying out the method (C) acid binding agents are organic bases. Preferably used such acid binding agents, such as tertiary amines, dialkylaminoalkyl and pyridine, such as, for example, triethylamine, 1,1,4,4-tetramethyl-Ethylenediamine, N, N - dimethylaniline, N,N-diethylaniline, pyridine, 4-dimethylaminopyridine, 1,4-diazabicyclo[2,2,2]octane and 1,8-diazabicyclo[5,4,0]-undec-6-ene.

Method (C) can be performed in the presence of the usual reactions of the catalyst. Examples of preferably used catalysts are: Quaternary ammonium salt, such as, for example, bromide of Tetramethylammonium, bromide of tetrapropylammonium, tetrabutylammonium bromide, bone, bromide butylpyrazine, bromide, heptylamine and chloride of benzyltriethylammonium: as well as complex krausova esters, such as, for example, dibenzo-18-crown-6, DICYCLOHEXYL-18-crown-6, 18-crown-6, [2,2,2] -cryptit, [2,1,1]- cryptit, [2,2,1]-cryptit, [2,2,3]-cryptit, [3,2,2]-cryptit.

When carrying out process (C) the reaction temperature can be varied within wide limits. The reaction is usually carried out at a temperature from about -76oC to about +50oC, preferably from 0oC to about 120oC.

Method (C) is usually carried out at atmospheric pressure, however, the reaction may and at elevated or reduced pressure.

When carrying out process (C), generally 1 mol derived chloropyridinyl formula (I) is subjected to interaction with 0.1 to 10 mol of halide compounds of formula (IV), and the reaction is carried out in the presence of a diluent and, if necessary, in the presence of an acid binding agent and catalyst. The product is processed by conventional methods.

Acid additive salts derived chloropyridinyl formula (I) can be obtained by ordinary methods of salt formation, for example, by dissolving the compounds of formula (I) in a suitable to become known by, for example by filtration, and, if necessary, be cleaned by rinsing with an inert organic solvent.

Thanks fungicidal activity proposed connection you can use for combating phytopathogenic fungi, such as, for example, plasmodiophoromycota, oomycetes, chytrids, records of Ascomycetes, zygomycetes, basidiomycetes and deuteromycete.

Thus, a further object of the invention is a means for combating phytopathogenic fungi, containing at least one carrier and the active substance, the active substance it contains a compound of the formula (Ia)

< / BR>
where Het' is a group of the formula

< / BR>
< / BR>
R1is hydrogen, unsubstituted or substituted alkyl with 1 to 6 carbon atoms, and substituents selected from the group comprising halogen, phenyl, cyano, alkoxy with 1 to 4 carbon atoms, alkylthio with 1 to 4 carbon atoms, alkylsulphonyl with 1 to 4 carbon atoms, alkoxycarbonyl with 1 to 4 carbon atoms, alkenyl with 2 to 4 carbon atoms, unsubstituted or substituted by alkoxycarbonyl with 1 to 4 carbon atoms; phenyl or unsubstituted or substituted 1 or 2 alkoxygroup with 1 to 4 carbon atoms, pyrimidinyl;

n is the number 1 or 2

or its acid-clusters of the formula (I') at a concentration of, necessary for combating phytopathogenic fungi, allows for the processing of parts of plants above the ground, the material for vegetative propagation and seed and soil.

Offer active compounds of the formula (Ia) (hereinafter: "active substance") can be converted to conventional preparations such as solutions, emulsions, wettable powders, suspensions, powders, foams, pastes, granules, tablets, sprays, impregnated with active compound of natural and synthetic substances, polymeric microcapsules used as the shell of the seed composition used incendiary device drugs, such as, for example, democommie cartridges, cans and coils, as well as cold or hot aerosol preparations intended for distribution in ultra-low volume.

These drugs get known techniques, for example, the travel of the active substances with extenders, i.e. liquid or liquefied gaseous or solid diluents or carriers, optionally with the use of surface-active agents, i.e. emulsifiers and/or dispersing agents and/or blowing agents. When using water as a filler and possibly the use of organic rusty or media used mainly aromatic hydrocarbons, as xylene, toluene or alkylnaphthalenes, chlorinated aromatic or aliphatic hydrocarbons, as chlorobenzene, chloroethylene or methylene chloride, aliphatic hydrocarbons like cyclohexane or paraffins, for example petroleum fractions, alcohols like butanol or glycol and also their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethylsulfoxide, and water.

Under liquefied gas diluents or carriers understand the liquids at normal temperature and atmospheric pressure gas, for example aerosol propellants, such as, for example, halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide.

As solid carriers used crushed natural minerals such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and crushed synthetic minerals such as highly disperse silicic acid, alumina and silicates. As solid carriers for granules are used, for example, crushed and fractionated natural rocks such as calcite, marble, PE is C organic material, such as sawdust, coconut shells corn cobs and stalks of tobacco.

As an emulsifier and/or blowing agent used, for example, nonionic and anionic emulsifiers, such as complex polyoxyethylene esters of the fatty acid series, simple polyoxyethylene esters of fatty alcohol series, for example, a simple alkylarylsulphonate ethers, alkyl sulphonates, alkyl sulphates, arylsulfonate, as well as protein hydrolysates.

As a dispersant is used, for example, ligninolytic spent liquor and methylcellulose.

The drugs can also use adhesives, such as, for example, carboxymethylcellulose and natural and synthetic polymers in the form of powder or granules, such as gum Arabic, polyvinyl alcohol and polyvinyl acetate.

The preparations may also contain colorants such as inorganic pigments, for example iron oxide, titanium oxide, Prussian blue, and organic dyes, as alizarin, azo and metallophthalocyanine dyes, and trace elements, such as metal salts, for example, salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.

The preparations contain as a rule 0.1 to 95 wt.%, predpochetaju or different work forms in the form of a mixture with other known active substances, such as, for example, fungicides, bactericides, insecticides, acaricides, nematicides, herbicides, deterring bird repellents, growth stimulants, nutrients and a means to improve soil quality.

The active substances can be used as such or in the form obtained by thinning drugs or ready-to-use forms, such as, for example, ready-to-use solutions, emulsions, suspensions, powders, pastes, granules. They are applied in the usual way, such as, for example, spraying, dipping, sputtering, spraying, evaporation, injection, education suspension, application brush, dusting, scattering, coating of the drug in a dry, wet or liquid state or in suspension, coating.

When processing parts of plants, the concentration of the active agent in the preparations can be varied within a wide range. Usually applied 1-0,0001 wt.%, preferably 0.5 to 0.001 wt.%.

Seed treatment is usually applied 0.001 to 50 g, in particular from 0.01 to 10 g of active substance per kilogram of seed.

When tillage is usually used the concentration of active principle in the treatment site, equal to within 0.00001-0.1 wt.%, in particular of 0.0001 to 0.02 wt.%.

Getting connect the thief 4.15 g of 1-methyl-1,2,4 - triazole in 300 ml of dihlormetilen. With stirring and ice cooling to a solution dropwise serves 10.6 g of the acid chloride 2,6 - dichlorophenylamino acid. The reaction mixture was stirred at room temperature for 8 hours After completion of the reaction, the reaction mixture was successively washed with aqueous 3% solution of hydrochloric acid, aqueous 3% sodium hydroxide solution and water. The organic layer is dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the resulting residue purified by column chromatography on silica gel using chloroform as eluent.

Obtain 4.7 g of 5-(2',6'-dichloro-4'-pyridylcarbonyl)-1-methyl - 1,2,4-triazole with a melting point 130,5 - 131, 5mmoC.

Example 2

< / BR>
to 5.1 g of triethylamine are served in a solution of 1.7 g of imidazole in 10 ml of pyridine. With stirring at a temperature of 0 to 10oC in a solution dropwise serves 10.6 g of the acid chloride 2,6-dichlorophenylamino acid. The reaction mixture was stirred at room temperature for 3 h Then the reaction mixture is poured in water of 7.5 n sodium hydroxide solution, and the mixture is heated under reflux for 1 h After the reaction, water is added, and the reaction mixture is cooled. Drop crystals that Sobir is,5 - 175oC.

Example 3

< / BR>
1.5 g of anhydrous potassium carbonate and of 1.23 g of Isopropylamine served in solution to 2.42 g of 2-(2',6'-dichloro-4'- pyridylcarbonyl)-imidazole in 50 ml of acetonitrile. The mixture for 6 hours, heated under reflux. After the reaction, water is added and extracted with methylene chloride. The organic layer is dried over anhydrous sodium sulfate, concentrated under reduced pressure and the resulting residue purified by column chromatography on silica gel using chloroform as eluent.

Obtain 1.8 g of 2-(2',6'-dichloro-4'-pyridylcarbonyl)-1 - isopropylimidazole.

The refractive index of nD20: to 1.5820.

Example 4

< / BR>
2,69 g of 5-(2',6'-dichloropyridine)-1-vinyl-1,2,4 - triazole with stirring at room temperature served in a solution of 4.3 g of periodate sodium and 0.05 g dioxide osmium in a mixture of 70 ml of dioxane and 20 ml of water. The mixture during the night stirred at room temperature. After the reaction, water is added and extracted with methylene chloride. The organic layer is dried over anhydrous sodium sulfate, concentrated under reduced pressure and the resulting residue purified by column chromatography on silica gel with clause the with melting point 155-158oC.

Example 5

< / BR>
1.5 g of anhydrous potassium carbonate and 1.4 g of methyliodide served in solution to 2.41 g of 3-(2', 6'- dichloropyridine)-1,2,4 - triazole in 50 ml of acetonitrile. The mixture for 6 hours, heated under reflux. After the reaction, water is added and extracted with methylene chloride. The organic layer is dried over anhydrous sodium sulfate, concentrated under reduced pressure and the resulting residue purified by column chromatography on silica gel using chloroform as eluent.

Get 1.5 g of 3-(2',6'-dichloropyridine)-1-methyl - 1,2,4-triazole with a melting point of 203 - 206oC.

Example 6

< / BR>
2.6 g of anhydrous tin tetrachloride served in a solution of 2.1 g of 2,6-dichloropyrimidine-4-carbonylchloride and 3 g of thiophene in 30 ml of nitromethane at room temperature. The mixture for 5 h heated under reflux. After the reaction the mixture is poured into 50 g of ice water and 10 ml of hydrochloric acid, then extracted three times with methylene chloride, taken in an amount of 50 ml Organic layer was washed with water and dried over anhydrous sodium sulfate. The solvent is distilled off and the crude product purified by column chromatography on silica gel using bonil)-thiophene with a melting point of 129 130oC.

Table 1 summarizes the compounds of formula (I) obtained by the above methods. Specified in table 1 of heterocyclic radicals are explained at the end of the table.

The fungicidal activity of the compounds of formula (Ia) is illustrated by the following examples.

Example 7: Test sprayed on the leaves of drug activity against pyricularia rice

Preparation containing compound drugs:

Active substance: 30 - 40 weight.h.

Media: mixture of diatomaceous earth and kaolin in the ratio of 1:5, 55 to 65 weight.h.

Emulsifier: a simple polyoxyethyleneglycol ether, 5 weight. h

Wettable powders are obtained by grinding into a powder and mixing the active substance, carrier and emulsifier, taken in the above amounts. Containing a specified amount of the active substance part of the wettable powder is diluted with water and subjected described in the next experience.

Implementation experience:

Seedlings of rice (cultivar: Kusabue) grown in vinyl pots with a diameter of 6 cm, Diluted to specified concentration of the solution of the active substance, taken in an amount of 25 ml per 3 pots, sprayed on the leaves of the seedlings will reach what's dispute Pyricularia oryzae sprayed on the seedlings, which to defeat stored at a temperature of 25oC and 100% relative humidity. 7 days after inoculation to determine the degree of destruction of plants in each vessel, and assess it on the following criteria. Calculate the reference value (%). At the same time check for phytotoxicity. The results are summarized in the following table 2. Specify in table 2 are average values of the results of the 3 pots.

The degree of destruction - the Percentage of the affected area (%)

0 - 0

0.5 to < 2

1 - 2 - <5
Reference value (%) = (1-(the degree of the damage of the treated plant - degree lesions untreated plants)) 100.

Note: In the examples 7 to 10 use the same methods for evaluating the degree of destruction and the calculation of control values

Example 8: Test appliciruemah on the surface of the drug on the activity against pyricularia rice

The implementation of the test:

Seedlings of rice (cultivar: Kusabue) at the stage 1.5 leaves irrigated transplanted into plastic pots with an area of 100 cm2one seedling in each pot. 7 days after perezhivanija when the seedlings are at the stage of 3 to 4 leaves, drug Razavi 10 ml/pot pipette dropwise serves on the surface of the water. 20 days after chemical treatment, the suspension is artificially cultivated dispute piricularia rice (fungus piricularia race C) is sprayed on the seedlings for lesions within 12 h store in inoculation mailbox at a temperature of 25oC and 100% relative humidity, and then in the greenhouse. 10 days after inoculation to determine the degree of destruction of plants in each vessel. Calculate the reference value (%). At the same time check for phytotoxicity. The results are summarized in the following table 2.

Example 9: Test sprayed on the leaves of drug activity against late blight of tomato

Preparation containing compound drugs:

Active substance: 30 - 40 weight.h.

Media: mixture of diatomaceous earth and kaolin in the ratio of 1:5, 55 to 65 weight.h.

Emulsifier: a simple polyoxyethyleneglycol ether, 5 weight.h.

Wettable powders are obtained by grinding into a powder and mixing the active substance, carrier and emulsifier, taken in the above amounts. Containing a specified amount of the active substance part of the wettable powder is diluted with water and subjected described in the next experience.

Khujand and grown in a greenhouse at a temperature between 15 25oC. the Preparation is diluted to the indicated concentrations of test compounds in quantities of 25 ml per 3 pots sprayed on small seedlings reached stage 4 leaves. 10 days after spraying zoosporangia in the affected areas, previously infected by the pathogen Phytophthora infestans, brush, wash in distilled water to prepare a suspension. The suspension is sprayed on the treated plants are then kept in a greenhouse at a temperature of 15 - 20oC. After 7 days after inoculation to determine the extent of the lesion in each pot and calculates the reference value. The results are average values of the results of the 3 pots. At the same time check for phytotoxicity. The results are summarized in table 2.

Example 10: the Test is sprayed on the leaves of drug activity against powdery mildew of barley

Implementation experience:

At about 10 grains of barley (cultivar: Haruna 2jo) sow in vinyl pots with a diameter of 7 cm and grown in a greenhouse at a temperature of 15 - 25oC. the Preparation is diluted to the indicated concentrations of test compounds obtained similar to example 9 by the way, in the amount of 25 ml per 3 pots sprayed on small seedlings, D. what about the infected with the pathogen Erysiphe graminis, sprinkle on the treated barley leaves. Plants kept in a greenhouse at a temperature of 15 - 20oC. After 7 days after inoculation to determine the degree of destruction of plants in each pot and calculates the reference value. The results are average values of the results of the 3 vessels. At the same time check for phytotoxicity. The results are summarized in table 2.

Derivatives chloropyridinyl formula I

< / BR>
where Het is a group of the formula

< / BR>
< / BR>
R1is hydrogen, unsubstituted or substituted alkyl with 1 to 6 carbon atoms, and substituents selected from the group comprising halogen, phenyl, cyano, alkoxy with 1 to 4 carbon atoms, alkylthio with 1 to 4 carbon atoms, alkylsulphonyl with 1 to 4 carbon atoms, alkoxycarbonyl with 1 to 4 carbon atoms; alkenyl with 2 to 4 carbon atoms, unsubstituted or substituted by alkoxycarbonyl with 1 to 4 carbon atoms; phenyl or unsubstituted or substituted 1 or 2 alkoxygroup with 1 to 4 carbon atoms, pyrimidinyl;

n = 1 or 2

and their acid additive salt.

2. Derivatives chloropyridinyl formula I on p. 1 where Het is a group of the formula

< / BR>
< / BR>
n = 1, and a chlorine atom is linked to position 2 or 6 peredelnoj group, or n = 2, and chlorine atoms Vasili substituted 1 - 3 identical or different substituents selected from the group comprising halogen, phenyl, cyano, alkoxy with 1 to 4 carbon atoms, alkylthio with 1 to 4 carbon atoms, alkylsulphonyl with 1 to 4 carbon atoms, alkoxycarbonyl with 1 to 4 carbon atoms; or R1alkenyl with 2 to 4 carbon atoms, unsubstituted or substituted by 1 to 3 same or different alkoxy with 1 to 4 carbon atoms; or R1is phenyl or pyrimidinyl, unsubstituted or substituted by 1 or 2 identical or different substituents selected from the group comprising methoxy, ethoxy.

3. Derivatives chloropyridinyl formula I on p. 1 where Het is a group of the formula

< / BR>
< / BR>
n = 1, and a chlorine atom is linked to position 2 or 6 peredelnoj group, or n = 2 and the chlorine atoms are associated with positions 2 and 6 peredelnoj group;

R1is hydrogen or alkyl with 1 to 4 carbon atoms, unsubstituted or substituted by 1 to 3 identical or different substituents selected from the group comprising halogen, phenyl, cyano, methoxy, methylthio, methylcarbamyl, tert. butylcarbamoyl, methoxycarbonyl, etoxycarbonyl, or R1alkenyl with 2 to 4 carbon atoms, unsubstituted or substituted by 1 to 3 methoxypropane, or R1is phenyl or pyrimidinyl, unsubstituted or Sensei least one carrier and an active ingredient, characterized in that the active substance it contains a compound of the formula Ia

< / BR>
where Het is a group of the formula

< / BR>
< / BR>
R1is hydrogen, unsubstituted or substituted alkyl with 1 to 6 carbon atoms, and substituents selected from the group comprising halogen, phenyl, cyano, alkoxy with 1 to 4 carbon atoms, alkylthio with 1 to 4 carbon atoms, alkylsulphonyl with 1 to 4 carbon atoms, alkoxycarbonyl with 1 to 4 carbon atoms; alkenyl with 2 to 4 carbon atoms, unsubstituted or substituted by alkoxycarbonyl with 1 to 4 carbon atoms; phenyl or unsubstituted or substituted 1 or 2 alkoxygroup with 1 to 4 carbon atoms, pyrimidinyl;

n = 1 or 2

or its acid additive salt in an effective amount.

Priority signs:

13.09.1995 - Het represents a five-membered heterocyclic ring containing 1 to 3 nitrogen atom;

21.06.1996 - Het represents thienyl.

 

Same patents:

The invention relates to new N-substituted azaheterocyclic carboxylic acids f-crystals (I) or their salts, in which R1and R2independently represent a hydrogen atom, halogen atom, trifluoromethyl, C1-C6-alkyl or C1-C6-alkoxy: Y is the grouporin which only the underlined atom participates in the cyclic system; X is a group-O-, -S-, -CR7R8, -CH2-CH2-, -CH=CH-CH2-, -CH2-CH=CH-, -CH2CH2CH2-, -CH=CH-, -NR9-(C= O)-, -O-CH2-, -(C= O)- or -(S=O)-, where R7, R8and R9independently represent a hydrogen atom or a C1-C6-alkyl; z = 1, 2, or 3; m = 1 or 2, n = 1 when m = 1 and n = 0 when m = 2; R4and R5each represents a hydrogen atom or, when m = 2, can both work together to develop a bond; R6is hydroxyl or C1-C8-alkoxygroup, or its pharmaceutically acceptable salt, provided that is not included compound 10-(3-(3-carbomethoxy-1-piperidyl) propyl) phenothiazines and 10-(3-(3-carborexics-1-piperidyl) propyl) phenothiazines

The invention relates to new derivatives of 1-[2-(substituted vinyl)]-5H-2,3-benzodiazepine, method of production thereof, pharmaceutical composition, method thereof and method of treating diseases of the Central nervous system

The invention relates to the derivatives of pyrazole and herbicides containing them

The invention relates to disubstituted polycyclic compounds, their derivatives, pharmaceutical preparations and methods of use in treating mammals disorders mental and/or neurological dysfunction and/or depressions such as diseases associated with degeneration of the nervous system, and not only their

The invention relates to anti-inflammatory and analgesic agents, in particular to the enol ester and ether prodrugs of 3-acyl-2-oxindole-1-carboxamides constituting a new class of well-known non-steroidal anti-inflammatory agents

The invention relates to new tetrahydropyridine - or 4-hydroxypiperidine-alkylation formula I, where R1, R2, R3and R6denote hydrogen, halogen, C1-C6-alkyl, C1-C6-perfluoroalkyl, C1-C6-alkoxyl or two adjacent radicals can form precondensation benzene ring, And denotes the carbon atom, and the dotted line denotes an optional bond, or a denotes a carbon atom that is associated with a hydroxyl group (C-OH), and the dotted line indicates the absence of coupling, n = 2 to 6, Z1, Z2and Z3represent a nitrogen atom or a substituted carbon atom, or a physiologically favourable salts, which possess antipsychotic or anxiolytic activity

The invention relates to novel triazole compounds of the General formula (1), where a denotes a linear or branched C1-C18-alkylenes group which may comprise at least one group which is selected from O, S, CONH, COO,3-C6-cycloalkene or double or triple bond; In denotes the radical of formula (a), (b) or (C); R1denotes H, NH2WITH3-C6-cycloalkyl or1-C8-alkyl, which is not substituted or substituted OS1-C8-alkyl; R2denotes H, HE, C1-C8-alkyl, C3-6-cycloalkyl, CF3, CN, NR3R4, SR3or CO2R3where R3denotes N or C1-C8-alkyl, a R4denotes H, C1-C8-alkyl, or COR3where R3stands WITH1-C8-alkyl; Ar represents naphthyl, phenyl with 1-2 substituent selected from C1-C8-alkyl, CF3, CHF2, NO2, SR3, SO2R3where R3means1-C8-alkyl; and pyridyl, pyrimidyl or triazinyl, which have from 1 to 3 substituents selected from C1-C8-alkyl, C2-C6-alkenyl, C2-C6-quinil, halogen, CN, CF3, OR4where R43-C6-lalouche possibly condensed, phenylalkylamine or 5-membered aromatic heterocycle with 1 to 2 nitrogen atoms, which may be condensed with a benzene ring

The invention relates to new N-substituted azaheterocyclic carboxylic acids f-crystals (I) or their salts, in which R1and R2independently represent a hydrogen atom, halogen atom, trifluoromethyl, C1-C6-alkyl or C1-C6-alkoxy: Y is the grouporin which only the underlined atom participates in the cyclic system; X is a group-O-, -S-, -CR7R8, -CH2-CH2-, -CH=CH-CH2-, -CH2-CH=CH-, -CH2CH2CH2-, -CH=CH-, -NR9-(C= O)-, -O-CH2-, -(C= O)- or -(S=O)-, where R7, R8and R9independently represent a hydrogen atom or a C1-C6-alkyl; z = 1, 2, or 3; m = 1 or 2, n = 1 when m = 1 and n = 0 when m = 2; R4and R5each represents a hydrogen atom or, when m = 2, can both work together to develop a bond; R6is hydroxyl or C1-C8-alkoxygroup, or its pharmaceutically acceptable salt, provided that is not included compound 10-(3-(3-carbomethoxy-1-piperidyl) propyl) phenothiazines and 10-(3-(3-carborexics-1-piperidyl) propyl) phenothiazines

The invention relates to Hinayana and hinokitiol, compositions containing them, and methods of producing these compounds

The invention relates to the derivatives of diphenylbutylpiperidine formula I where n is 1 or 2, or pharmaceutically acceptable salts

The invention relates to new derivatives of benzylpiperidine formula I, where R1denotes H or Hal, R2is unsubstituted or substituted Gal in the aromatic ring of the benzyl group in the 2 -, 3-or 4-position piperidino ring, provided that R2doesn't mean 4-benzyl when X represents-CO-, Y -, and Z represent CH2and R1- N; R3denotes H or A , X IS-CO-, Y is --CH2-, -NH - or-O-, Z is-CH2- or connection, And - alkyl WITH1-6In - OH, H+, HE, Hal Is F, Cl, Br or I, and their salts
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