Fungicidal composition, derivatives triazolopyrimidine, the retrieval method and the method of combating fungi

 

(57) Abstract:

The invention relates to fungicidal compositions, a new derivative of triazolopyrimidine, method of production thereof and method of combating fungi. Describes fungicidal composition comprising an active component derived triazolopyrimidine and media. As specified derivative it contains an effective amount triazolopyrimidine compounds of General formula I, in which R represents a C1-C6-alkyl, C1-C6-alkoxygroup, C3-C8-cycloalkyl group; phenyl substituted by 1-3 substituents selected from halogen atoms, C1-C4-alkyl, C1-C4-halogenoalkane, C1-C4-alkoxy, C1-C4-halogenoalkane, halogenmethyl, phenyl, phenoxy and benzyloxy; C1-C4-alkoxy, fenoxaprop substituted by a halogen atom or C1-C4-alkyl; naphthyl or thienyl; Hal - atom CL or Br. Describes how to obtain the derivative triazolopyrimidine formula I consists in the fact that the compound of General formula II, where the value R is defined paragraphs. 5 and 6 formula, is subjected to the interaction with glorieuses or brainwashin agent. Way of dealing with grinnie applies to some of dehalorespiration, some of which are new, methods for their preparation, to compositions containing such compounds, and their use as fungicides.

Chemical Abstracts (1964), 61:2941 disclose the receipt of 5,7-sodium dichloro-6-methyl-1,2,4-triazolo [1,5-a] pyrimidine heating 5,7-dihydroxy-6-methyl-1,2,4-triazolo [1,5-a] pyrimidine with phosphorus oxychloride for 4 hours at 100oC. However, there is no indication that any of these compounds have biological activity.

The European application, the applicant N 92204097.7 (EP-A-0550113), pending, discloses compounds of General formula

< / BR>
in which R3represents a possibly substituted aryl group, and X and Y both represent a chlorine atom or a bromine atom,

as intermediate compounds in getting some fungicide active derivatives of triazolopyrimidine General formula

< / BR>
in which R1represents a possibly substituted alkyl, alkenylphenol, alkenylphenol, akadeemiline, cycloalkyl, bicycloalkyl or heterocyclyl group, R2represents a hydrogen atom or alkyl group; or R1and R2together with the nitrogen atom represent a possibly substituted heterocyclic ring; R3is C is e R5represents a hydrogen atom or a group: amino, alkyl, cycloalkyl or bicycloalkyl and R6represents a hydrogen atom or alkyl group.

However, in this document there is no indication that the compounds of formula A have any fungicidal activity.

Now it is revealed that some compounds of formula A and some other new derivatives dehalorespiration manifest themselves fungicidal activity.

In accordance with the invention offers a fungicidal composition which contains a carrier and, as active ingredient a compound of General formula I

< / BR>
in which R represents a possibly substituted alkyl group or an alkoxy group with a straight or branched chain, or perhaps replaced cycloalkyl, aryl, aryloxy or heterocyclyl group; Hal represents an atom of fluorine, chlorine, bromine or iodine.

When the compounds in the compositions of this invention contain cycloalkyl group, it may contain from 3 to 8, preferably from 3 to 6 carbon atoms. Aryl group may be any aromatic hydrocarbon group, more phenyl or naftalina group. Heterocyclyl a group 3-6 membered ring is preferable, and especially 5 - and 6-membered rings. Better if it is a nitrogen-, oxygen - or sulfur-containing rings, such as pyridinyl, pyrimidinyl, pyrrolidinyl, furyl, Pirelli, morpholinyl and thienyl.

If any of the above substituents listed as possible (optional) substituted by substituent groups that may be present, can be any one or more of the groups commonly used in obtaining pesticide compounds and/or modification of such compounds to influence their structure/activity, stability, permeability, or other property. Specific examples of such substituents include, for example, halogen atoms, nitro, cyano, Tiziana, cyanate, hydroxyl, alkyl, haloalkyl, alkoxy, haloalkoxy, amino, alkylamino, dialkylamino, formyl, alkoxycarbonyl, carboxyl, alcoholnye, alkylthio, alkylsulfonyl, alkylsulfonyl, glossiphoniidae, carbamoyl, alkylamino, phenyl, phenyloxy, benzyl and benzyloxy, heterocyclyl, especially foreline, and cycloalkyl, in particular, cyclopropyl group. Can usually be 0-3 Deputy.

If any of the mentioned substituents represent or contain alkyl group, it may be the data of the substituents represents or contains an aryl or cycloalkyl part, aryl or cycloalkyl part may itself be substituted by one or more halogen atoms, nitro, cyano, alkyl, haloalkyl, alkoxy or haloalkoxy groups. If cycloalkyl and heterocyclyl groups of possible substituents include groups which together with two adjacent carbon atoms cycloalkyl or heterocyclyl group form a saturated or unsaturated hydrocarbon ring. In other words, a saturated or unsaturated hydrocarbon ring may be condensed with cycloalkenes go heterocyclyl group.

Better, if R represents a C1-12alkyl, C1-C12alkoxy, C3-8cycloalkyl, phenyl, phenoxy or naftalina group or a 3-6-membered heterocyclic ring, each group or ring may be replaced by one or more substituents selected from: halogen atoms, nitro, cyano, hydroxy, C1-4alkyl, C1-4haloalkyl, C1-4alkoxy, C1-4haloalkoxy, amino, C1-4alkylamino, di-C1-4alkylamino, formyl, C1-4alkoxycarbonyl, carboxyl, glossiphoniidae, phenyl, phenoxy, benzyl and benzyloxy groups, or if R present is Yu with the benzene ring.

Even better, if R represents a C1-6alkyl, C1-6alkoxy, C3-8cycloalkyl, phenyl, phenoxy or naftalina group or a 3-6-membered heterocyclic ring, each group or ring may be replaced by one or more substituents selected from halogen atoms, C1-4of alkyl, C1-4haloalkyl, C1-4alkoxy, C1-4haloalkoxy, halosulfuron, phenyl, phenoxy and benzyloxy groups.

A preferred subgroup of compounds of formula I is a subgroup, in which R represents through boutelou, ethoxy, cyclopentyloxy, tsiklogeksilnogo, forefeeling, chloroanilino, bromoaniline, dichloroaniline, chloropropanediol, methylphenylene, propylaniline, butylaniline, dimethylaniline, triftormetilfullerenov, metoksifenilny, ethoxyphenyl, dimethoxyaniline, diethoxyaniline, trimethoxyaniline, triphtalocyaninine, chlorosulfonylphenyl, biphenylyl, phenoxyphenyl, benzyloxyphenyl, perience, chlorophenoxy, methylphenoxy, dimethylphenoxy, naftalina or thienyl group; and Hal represents a chlorine atom or bromine.

It is also proposed a method of obtaining a composition which includes a member of one compound or a mixture of several compounds of the present invention.

The composition according to the invention preferably contain from 0.5 to 95 wt.% the active ingredient.

A carrier in a composition according to the invention can be any material which is the active ingredient in order to facilitate the application in the treated lesion (locus), which, for example, is a plant, seed or soil, or to facilitate storage, transport or handling. The carrier may be solid or liquid, including a material which under normal conditions gas, but may be compressed to form a liquid, using any of the commonly used media in obtaining fungicidal compositions.

Suitable solid carriers include natural and synthetic clays and silicates, for example natural silicas such as diatomaceous earth; magnesium silicates, for example, only; magnesium aluminum silicates, for example, attapulgite and vermiculite; aluminum silicates, for example kaolinites, montmorillonite and micas; calcium carbonate; calcium sulphate; ammonium sulphate; synthetic hydrogenated silicon oxides and synthetic calcium silicates or aluminum; elements, for example carbon and sulphur; natural and synthetic resins, for example, coumarone resins, povoski, paraffin wax, and chlorinated mineral waxes; and solid fertilizers, for example superphosphates.

Suitable liquid carriers include water; alcohols, such as isopropanol and glycols; ketones, for example acetone, methyl ethyl ketone, methylisobutyl ketone and cyclohexanone; ethers; aromatic or aliphatic hydrocarbons, such as benzene, toluene and xylene; petroleum fractions, such as kerosene and light mineral oils; chlorinated hydrocarbons such as carbon tetrachloride, perchloroethylene and trichloroethane. Acceptable well as mixtures of different liquids.

Fungicidal compositions are often formed and transported in a concentrated form, which is then diluted by the user before application. The presence of small amounts of media, which is a surfactant that facilitates this method of dilution. Therefore it is better to have at least one carrier in the composition of the invention was surfactants. For example, the composition may contain at least two carriers, at least one of which is a surfactant.

The surfactant may be an emulsifying, dispersing or wetting agent; it may be nonionic or ionic. Examples of suitable surfactants include on the t or aliphatic amides or amines, containing at least 12 carbon atoms in the molecule with ethylene oxide and/or propylene oxide; fatty acid esters of glycerol, sorbitan, sucrose or pentaerythritol, and their condensates with ethylene oxide/propylene oxide; condensation products of fatty alcohols or alkyl phenols, for example, n-op or n-octelnet, with ethylene oxide and/or propylene oxide; sulfates or sulfonates of these condensation products, salts of alkaline or alkaline earth metals, preferably sodium salt, esters of sulfuric or sulfo-acid containing at least 10 carbon atoms in the molecule, for example, sodium lauryl sulfate, foralkyl sulfates of sodium, sodium salts of sulfonated castor oil and sodium alkylated sulfonates, such as dodecylbenzenesulfonate; and polymers of ethylene oxide and copolymers of ethylene oxide and propylene oxide.

Compositions of the invention can be formulated, for example, as wettable powders, dusty, granules, solutions, mulgirigala concentrates, emulsions, suspension concentrates and aerosols. Wettable powders usually contain 25, 50 or 75 wt.% the active ingredient and in addition to solid inert carrier usually contain 3-10 wt.% dispersing agent, etc what do you usually plotted as a dust concentrate composition, similar composition wettable powder but without a dispersant chemical, and can be thinned on the field other solid media to obtain a composition containing 0.5-10 wt.% the active ingredient. The size of the granules is typically 10-100 BS mesh (1,676-0,152 mm), and are produced by technology agglomeration or impregnation. Usually pellets containing 0.5-75 wt.% the active ingredient and 0-10 wt.% additives, such as stabilizers, surfactants, slow release modifiers and binding agents. The so-called dry flowable powders consist of relatively small granules with a relatively high concentration of the active ingredient. Mulgirigala concentrates usually contain, in addition to the solvent and, if necessary, co-solvent, 1-50 weight. %/about. the active ingredient, 2-20 wt.%/about. emulsifiers and 0-20 wt.%/about. other additives, such as stabilizers, penetrants and corrosion inhibitors. The composition of the suspension concentrates, in order to obtain stable not deposited flowable product comprises 10-75 wt.% the active ingredient, 0.5 to 15 weight. % of dispersing agents, 0.1 to 10 wt.% suspendida agents such as protective colloids and thixotropic agents, 0-10 wt.% other additives, such as preventing the formation of foam inhibitors is dient practically insoluble; some solid organic substances or inorganic salts may be present dissolved in the product, to prevent sedimentation or as antifreeze agents for water.

Aqueous dispersions and emulsions, for example compositions obtained by diluting wettable powder or concentrate according to the invention with water, also included in the scope of the invention. These emulsions can be of the type water-in-oil or oil-in-water and can have the consistency of mayonnaise.

Compositions of the invention can contain other ingredients, for example, other compounds possessing herbicide, insecticide or fungicide properties.

Of particular interest in extending the protective activity of the compounds of the invention is the use of media that will provide a slow release of antifungal compounds in the environment plants in need of protection. These drugs slow release may be injected into the soil at the roots of the vine, or may include an adhesive component, that can be used directly on the stem of the vine.

Some of the compounds of formula I, as defined above, are new. Accordingly, the invention provides the ilen group possibly substituted, both groups Hal does not represent a chlorine atom or a bromine atom, and

(ii) if R is a methyl group, both groups Hal does not represent a chlorine atom.

Further, the present invention provides a method of obtaining the compounds of formula I, as defined above, which includes

a) the reaction of compounds of General formula

< / BR>
in which R is as defined above,

with glorieuses or brainwashin agent to obtain a compound of the formula I, in which Hal represents a chlorine atom or bromine;

b) if desired, the reaction of the compounds of formula I, obtained in stage (a) with a fluorinating agent to obtain a compound of the formula I, in which Hal represents a fluorine atom; and

c) if desired, the reaction of the compounds of formula I, obtained in stage (a), with NH3and then diiodomethane in the presence diastereomer agent to obtain a compound of the formula I, in which at least one Hal represents an atom of iodine.

The way the stage (a) can be carried out in the presence of a solvent. Suitable solvents include halogenated hydrocarbons such as dichloromethane. In addition, excess glorieuses or brainwashes agent may serve as a solvent. Suitable gloriouse agents include oxyl Rome phosphorus. The reaction is carried out at a temperature in the range of 0oC to the reflux temperature of the reaction mixture, the preferred reaction temperature is from 20oC to the reflux temperature of the reaction mixture.

The way the stage (b) is carried out in the presence of a solvent. Suitable solvents include sulfolane, dimethylformamide or a mixture of acetonitrile and crown ether. If the solvent is used sulpholane or dimethylformamide, as a co-solvent is good to use toluene, with the aim of degidrirovaniya fluorinating agent. The reaction is usually conducted at a temperature in the range from room temperature (about 15oC) to a temperature of phlegmy the reaction mixture, the preferred reaction temperature is from 40oC to the temperature of phlegmasia the reaction mixture. Suitable fluorinating agents include fluorides of alkali metals, especially potassium fluoride, pentaploid antimony TRIFLUORIDE and diethylaminoethyl.

Reaction with NH3in the way of stage (c) is carried out in the presence of a solvent. Suitable solvents include ethers, such as dioxane, diethyl ether and tetrahydrofuran, halogenated hydrocarbons, such as dichloromethane, and, especially, tawainese, the preferred reaction temperature is from 40oC to temperature phlegmy the reaction mixture. It is also desirable that the reaction was carried out in the presence of a base, and an excess of NH3can serve as a basis. Diastereomer agent used in stage (c) may be any alkilany ester of nitrous acid, it is better to take isopentyl nitrite. If you are using alkilany ester of nitric acid, it can serve as a co-solvent with diiodomethane. This reaction is carried out at a temperature of from 60oC to 120oC, and preferably from 70oC to 110oC. Both phases in the way of stage (c) can be performed in one reactor.

The compounds of formula II can be obtained by reaction of 3-amino-1,2,4-triazole with the corresponding ester of malonic acid under alkaline conditions according to the method of Y. Makisumi, Chem.Pharm. Bull. 9, 801, (1961).

Further the invention proposes the use as a fungicide compounds of General formula I, as defined above, or a composition as described above, and a method of combating fungi in the hearth (locus), which includes treatment center that can be, for example, plants exposed to fungi, seeds of such plants or the medium in which to grow these plants, or will grow, the same is s, such as wheat, oats, apples and tomatoes. The term of protection usually depends on the selected connection, and on many external factors such as climate, the impact of which is usually mitigated by use of a suitable drug.

Further, the invention is illustrated by the following examples.

Example 1.

Getting 5,7-sodium dichloro-6-(2-chlorophenyl)-1,2,4-triazolo[1,5-a]pyrimidine

(R = 2-chlorophenyl; Hal=Cl)

Mixed 5,7-dihydroxy-6-(2-chlorophenyl)-1,2,4-triazolo [1,5-a] -pyrimidine (6.2 g, 0,026 M) and 30 ml of phosphorus oxychloride, and the resulting suspension was maintained at tophlegmy 3 hours. The excess phosphorus oxychloride drove from received net of the solution and the resulting viscous oil was dissolved in 50 ml of dichloromethane. For the decomposition of trace impurities of phosphorus oxychloride in dichloromethane solution was slowly added 50 ml of ice water. Then the organic layer was separated, dried with sodium sulfate and the solvent is kept in vacuum to obtain 6,62 g of 5,7-sodium dichloro-6-(2-chlorophenyl)-1,2,4-triazolo-[1.5A]-pyrimidine in the form of yellowish crystals, so pl. 153oC.

Yield: 85% of theoretical.

Example 2. Getting 5,7-dibromo-6-(2-chlorophenyl)-1,2,4-triazolo [1.5 a]-pyrimidine

(R = 2-chlorophenyl; H is the temperature of about 100oC molten oxybromide phosphorus (excess, 40 g). After a vigorous initial reaction was clean, very viscous oil, which was left at 120oC for 2 hours. The mixture was cooled to room temperature and the obtained glass portions was added to a mixture of water and dichloromethane. The organic layer was separated sodium sulfate and the solvent is kept in vacuum to obtain 19.93 per g of 5,7-dibromo-6-(2-chlorophenyl)-1,2,4-triazolo [1,5-a]-pyrimidine in the form of yellowish crystals, so pl. 212oC.

Output: 90% of theoretical.

Examples of 3 - 52.

Ways, similar to that described in example 1 above were obtained with other compounds of the invention listed in table. 1 at the end of the description. In this connection table is specified with reference to formula I.

Example 53.

The fungicidal activity of the compounds according to the invention was investigated in the following tests.

(a) Antispammeta activity against downy mildew of grape (Plasmopara viticola; PVA).

Test direct destruction of spores using a spray on the leaves. The lower surface of leaves all vines (Cabernet Sauvignon) were inoculable spraying a water suspension containing 2.5 104for premises with high humidity, then 24 hours when the greenhouse temperature and humidity. On the lower surface of infected leaves was sprayed a solution of active material in water/acetone 1:1, containing 0.04 to "TWEEN 20" (Tob. mark; surfactant - polyoxyethylene ether sorbitan). Plants were treated with the use of automatic lines and spray nozzles. The concentration was 1000 frequent/mill. in volume spray - 700 l/ha After spraying, the plants were returned to normal greenhouse conditions for 96 hours and then transferred into the room with high humidity for 24 hours for the initiation of sporulation to evaluate the results. The evaluation was conducted based on the percentage of leaf area covered with spores in comparison with the control plants.

(b) Direct protection against late blight of tomato (Phytophthora infestans; PIP).

Test for direct protection spray on the leaves. On the upper leaf surface of tomato released with two leaves were sprayed tested the connection with a dosage of 1000 frequent/mill. using a spray gun, as described in (a). After an appropriate period of 24 hours under normal greenhouse conditions the upper leaf surface was inoculable spraying a water suspension containing 2 to 105zoospores/ml is for growth. The assessment was based on the interest rate of the affected leaf area compared to control leaves.

(c) Direct protection against downy mildew of grapes. (Plasmopara viti cola; PVP).

The test is a direct test using a spray on the leaves. On the lower surface of leaves whole plant grapes (Cabernet Sauvignon) was sprayed testwave connection with dosage 1000 frequent/mill. using automatic line sputtering as described in (a), and after a subsequent period of 24 hours under normal greenhouse conditions the lower leaf surface was inoculable spraying a water suspension containing 2.5 104zoosporangium inside host/ml Inoculated plants were kept for 24 hours in a room with high humidity, 5 days under normal greenhouse conditions, and then returned in 24 hours in conditions of high humidity. The evaluation was conducted on the proportion of leaf area covered with spores in comparison with the area on the control sheets.

(d) Activity against early rot of tomato (Alternaria solani; AS)

This test determines the contact preventive activity testremove compounds used in the form of spray on the leaves. Sprouts tomatoes (Outdoor Girl) were grown coy line spray, as described in (a). Asthemia compounds were applied as a solution or suspension in a mixture of acetone and water (50:50 vol/vol), containing 0,04 surfactant (TWEEN 20" - Tov. a sign). One day after treatment, the shoots were insulinomas by sputtering on the upper surface of the leaf suspension A. Solani conidia containing 104spores/ml 4 days after inoculation the plants were kept moist in a humid room at the 21oC. Disease was assessed 4 days after inoculation based on the percentage of the surface area of the sheet covered by the defeat.

(d) Direct protective activity against gray mold of beans (Botrytis cinerea; BCB).

The test determines the direct protection spray on the leaves. The upper surface of leaves of bean plants (Sutton ) was subjected to sputtering testujemy connection with dosage 1000 frequent/ mill. using automatic spray installation as described in (a). 24 hours after spraying the leaves insulinomas with an aqueous suspension containing 105conidia/ml 4 days after inoculation the plants were kept moist in a moist room at a temperature of 21oC. Disease was assessed 4 days after inoculation based on the percentage of the surface area of the sheet, Oh what I direct therapeutic test, use the spray on the leaves. Leaves of wheat (Norman) on stage one leaf insulinomas by spraying aqueous suspensions containing 1 to 106spores/ml Inoculated plants were kept for 24 hours in a room with high humidity before processing. Plants were sprayed solution testremove connection with dosage 1000 frequent/mill, using automated spray will set as described in (a). After drying, the plants were maintained for 6-8 days at 22oC and moderate humidity, was then evaluated. The evaluation was based on the density of lesions per leaf compared with the leaves of the control plants.

(g) Activity against brown rust of wheat (Puccinia recondita; PR).

The test is a direct protective spray on the leaves. Wheat germ (Avalon) were grown to stage 1-1,5 sheet. Then the plants were sprayed testwave connection with dosage 1000 frequent/mill. using automatic spray installation as described in (a). Asthemia compounds were applied as a solution or suspension in a mixture of acetone and water (50:50 vol/vol), containing 0,04 surfactant (TWEEN 20 " - Tov. a sign). After 18-24 hours after treatment, the shoots were inoculators spray on plants from all sides aqueous spore, suspense is gnosti at a temperature of 20-22oC. the plants were kept in greenhouse conditions similar to the environment, i.e. at moderate relative humidity and at a temperature of 20oC. Disease was assessed 10 days after inoculation based on the percentage of space the plants covered sporulating pustules, in comparison with the control plants.

(h) Activity against powdery mildew of cereals (Erysiphe graminis f.sp hordei; EG).

The test is a direct therapeutic test applying the spray to the leaves. The leaves of sprouts oats (Golden Promise) were inoculators applying dust conidia of powdery mildew on the day before treatment testujemy United. Inoculated plants were kept overnight under normal greenhouse temperature and humidity prior to treatment. Plants were sprayed testwave connection with dosage 1000 frequent/mill. using automatic spray installation as described in (a). After drying, the plants were returned to room temperature 20-25oC and moderate humidity for up to 7 days, then were evaluated. The evaluation was based on the interest rate of the leaf area covered with sporulation compared with leaves on control plants.

(i) the m spray on the leaves. On leaves of rice sprouts (Aichiaishi about 30 shoots per pot) was sprayed aqueous suspension containing 105spores/ml for 20-24 hours prior to processing testujemy connection. Inoculated plants were kept overnight in high humidity and then gave them to dry before spraying testremove connection with dosage 1000 frequent/mill. using automatic spray installation as described in (a). After treatment the plants were kept in the room, special for rice cultivation at 25-30oC and high humidity. The evaluation was conducted after 4-5 days after treatment and was based on the density of necrotic lesions on the leaf in comparison with the control plants.

(j) the Activity against Glazkova blotch of wheat in vitro (Pseudocercosporella herpotrichoides; PHI).

This test determines the in vitro activity of compounds against fungi causing leaf spot of wheat. Testwave compound is dissolved or suspendered in acetone and added to 4 ml aliquots diluted in half of the broth potato dextrose placed in Petri dishes with 25 cells with a final concentration of 50 frequent/mill. connection and 2.5% acetone. Each cell was inoculates a piece of agar/tipredane mycelial growth.

(k) Activity against in vitro Fusarium (Fusarium culmorum; FSI).

This test determines the in vitro activity of compounds against Fusarium species that cause rotting of the stem and roots. Testwave compound was dissolved or suspendibility in acetone and was added to the molten agar potato dextrose in half concentration with a final concentration of 50 frequent/mill. connection and 2.5% acetone. After solidification of the agar Cup was inoculable pieces of agar and mycelium diameter 6 mm, taken from 7-day cultures of Fusarium sp. The cups were incubated at 20oC 5 days and was determined radial growth from the pieces.

The degree of suppression of the disease in all the above tests were expressed in percentage compared with either untreated control objects control objects, spray diluent criteria:

0 - the suppression of the disease less than 50%,

1 - the suppression of the disease by 50 - 80%,

2 - the suppression of the disease by more than 80%.

The results of these tests are given in the table. II at the end of the description.

Example 54.

(a) Antispammeta activity against powdery mildew of grape (Plasmopara viticola; PVA).

The test is the (Gabernet Suavignon) height of approximately 8 cm inoculated aqueous suspension, containing 5 to 104zoosporangium inside host/ml Inoculated plants are kept for 24 hours at 21oC in the room with high humidity, then 24 hours in the greenhouse at 20oC and a relative humidity of 40%. On the lower surface of infected leaves sprayed solution testremove compounds in 1:1 water/acetone containing 0.04% of "TWEEN 20". Plants are sprayed from the spray port with two nozzles. The concentration is 600 frequent/mill. and the amount of spray - 750 l/ha After drying, the plants are returned to the table at 20oC and 40% relative humidity for 96 hours and then transferred into the room with high humidity for 24 hours for induction of sporulation. The assessment is based on the interest rate of the leaf area covered with spores in comparison with spores on the test sheets.

(b) Direct protective activity against late blight of tomato (Phytophthora infestans; PIP).

This is a direct protective test using the spray on the leaves. On tomato plants with two sprouted leaves (First in the Field sprayed testwave connection with dosage 600 frequent/mil., as described in (a). After drying, the plants are kept for 24 hours in the greenhouse at 20oC and 40% relative humidity. Then the upper prestine kept for 24 hours at 18oC in high humidity areas, and then 5 days in the growing chamber 15oC and 80% relative humidity with a 14 hours day length. The assessment is based on the interest rate of the affected leaf area compared to the area on the control sheets.

(c) Activity against early blight of tomato (Alternaria solani; AS).

This is a direct preventive test applying the spray on the foliage. Sprouts tomatoes (Outdoor Girl) at the stage of deployment of the second sheet are subjected to sputtering testujemy connection with dosage 600 frequent/mil., as described in (a). After drying, the plants are kept for 24 hours in the greenhouse at 20oC and 40% relative humidity followed by inoculation of the upper surfaces of the leaves with an aqueous suspension of conidia of A. solani containing 1 to 104conidia/ml After 4 days of being in the room with high humidity in the 21oC assessment of disease proportion of the surface area of the sheet covered by the defeat in comparison with the control plants.

(d) Direct protective activity against gray mold (Botrytis cinerea; BCB).

This is a direct protective test using spray on the foliage. Plant beans (Sutton ) with two pairs of leaf water was maintained for 24 hours in the greenhouse at 20oC and 40% relative humidity. Then the upper surface of leaves was inoculates water suspension containing 1 to 106conidia/ml, the Plants were maintained for 4 days at 20oC in high humidity areas. The evaluation was conducted on the proportion of leaf area affected by the disease compared to the area on the control sheets.

(e) Activity against blotch of wheat (Leptosphaeria nodorum; LN).

This is a direct therapeutic test with the use of spray on the foliage. Wheat germ (Norman) at the stage of a single sheet, inoculants water suspension containing 1.5 to 106conidia/ml Inoculated plants are kept for 24 hours at 20oC in high humidity areas, with subsequent spray testremove connection, as described in (a). After drying, the plants are 6-8 days in the greenhouse at 22oC and 70% relative humidity. The evaluation is conducted on the density of lesions per leaf compared with lesions in the leaves of control plants.

(f) Activity against Glazkova spot in vitro wheat (Pseudocercosporella herpotrichoides; PHI).

This test determines the in vitro activity of compounds against fungi causing ocellar spot of wheat. Testwave solo dextrose with half concentration, placed in Petri dishes with 25 sections with a final concentration testremove connection with 10 frequent/mill and acetone 0.825% of the Fungal inoculum consists of fragments of mycelium of P. herpotrichoides grown in broth potato dextrose with half concentration in shake flasks, and he was added to the broth in an amount of 5 to 104fragments of mycelium/ml of broth. Petri dishes were incubated at 20oC 10 days before evaluation of mycelial growth.

(g) Activity against Rhizoctonia in vitro (Rhizoctonia solani; RSI).

The test determines the in vitro activity of compounds against Rhizoctonia solani, which causes rotting of the roots and stems. Testwave compound is dissolved or suspendered in acetone and added to a 4 ml aliquot of the broth potato dextrose with half concentration, which is bottled in Petri dishes with 25 sections to obtain the final concentration of the compound in 10 frequent/mill and acetone 0,825%. The fungal inoculum consists of mycelial fragments of R. solani grown in broth potato dextrose with half concentration in flasks for crops, and added to the broth in an amount of 5 to 104fragments/ml of broth. Petri dishes are incubated at 20oC 10 days to determine growth in the vitro activity of compounds against Venturia inaequalis, which causes parse Apple trees. Testwave compound is dissolved or suspendered in acetone and added to a 4 ml aliquot of the broth potato dextrose with half concentration, which is bottled in Petri dishes with 25 sections to obtain the final concentration of the compound in 10 frequent/mill. and acetone 0,825%. The fungal inoculum consists of mycelial fragments and spores of V. inaequalis grown on malt agar and added to the broth in an amount of 5 to 104stages/ml of broth. Petri dishes are incubated at 20oC 20 days to assess the growth of the mycelium. The degree of suppression of the disease in all the above tests are expressed as compared with the untreated control objects or with the control objects processed diluent, in accordance with criteria:

0 = suppress disease less than 50,

1 = suppress disease by 50-80%,

2 = the suppression of the disease by more than 89%.

The results of these tests are given in the table. III at the end of the description.

Example 55.

Determination of MIC values (Minimum concentration suppressing compounds against various phytopathogenic fungi.

The MIC values were determined by tests serial razbavleniya and distribution in the wells was carried out by the robot processor TECAN RSP 5000.

Compounds were diluted to the following concentrations: 100, 50, 25, 12,5, 6,25, 3,13, 1,56, 0,78, 0,39, 0,20, 0,10 and 0.05 g/ml

To obtain the nutrient solution V8 juice (Tov. mark) was kind of balanced out by the calcium carbonate and centrifugals. Pop-up (supernatants) layer was diluted with distilled water (1:5) to the final concentration.

Fungi (Alternaria solani, Botrytis cinerea, Pseudocercosporella herpotrichoides, Micronectriella nivalis, Gaeumannomyces graminis) was added to the wells of a drop of spore suspension. Then microtiter tablets were incubated at 20oC 6 - 8 days. The value of the MIC is the lowest concentration in a series of dilutions without mycelium growth was determined by visual inspection of tablets.

The results of these tests are given in the table. IV at the end of the description.

Example 56.

Determination of the minimum concentration suppression testweek compounds in the test serial dilution with phytopathogenic fungi Alternaria solani, Botrytis cinerea, Rhizoctonia solani.

Test serial dilution was performed using microtiter tablets with 24 or 48 holes on the tablet. Asthemia compounds were used in the form of 1000 g/ml aqueous suspension containing 20% of acetone, which is then sterile filtered through a 0.2 filter. Dilution by the use of robot-processor TECAN RSP5000. Range testweek concentration was 100 g/ml to 0.05 g/ml was Done 12 dilutions. Nutrient solution was chosen in accordance with the dietary needs of a pathogen.

The inoculum was added drop (50 l) of the spore suspension (5 to 108) ml in the wells.

Assessment

After 6-12 days incubation at suitable temperatures, the MIC value was determined by visual assessment. The lowest concentration in the range of dilution without mycelium growth was defined as the MIC value. The results presented in table. V at the end of the description.

Example 57.

Field test Cercospora arachidicola on peanut.

15 seeds peanuts were planted in pots filled with soil substrate. When the plants have released 4 true leaves (approximately 12-14 days after sowing) they were processed from hand-held spray fungicides and tostuemyi connections. Asthemia compounds were used with a concentration of 500 g/ml in a mixture containing 10% acetone and 0.05% Tritor X-155 in water. The total number of spray mixture corresponds to 1000 l/ha For processing used 6 pots. 2 days after treatment, the pots were exhibited in the box next to the peanut plants on which the fungus Cercospora arachidicola formed parts of sporulate. power was calculated using the formula of Abbott.

Field test on Puccinia arachidis on peanuts.

15 seeds peanuts were planted in pots filled with soil substrate. When the plants have released 4 true leaf, they were processed from hand-held spray fungicides and tostuemyi connections. Asthemia compounds were used with a concentration of 500 g/ml in a mixture containing 10% acetone and 0.05% Triton X-155 in water. The total number of spray mixture corresponds to 1000 l/ha For processing was done in 6 iterations. 2 days after treatment, the pots were exhibited in the box next to the plants, the leaves of which the fungus Puccinia arachidis formed spirulina pustules. The assessment was performed 19 days after treatment definition percentage of infected leaf area. Percent efficacy was calculated using the formula of Abbott.

The results presented in table.VI.

Examples of the compositions.

Example A.

Suspension concentrate (SC).

The active component is the Compound N 37 100.0 g

Anionic surfactants - MorwetD4251)25,0 g

Dispersing agent is PluronicPE 105002)5.0 g

Biocide - ProxelCXL3)1.5 grams

Antifoam - Rhodorsil4264)>/BR>The distribution of particle size - particle Size [Ám]

x10 - 0,78

x50 - 1,95

x90 - to 4.52

The density PR 20oC: 1,053 g/ml

Appearance: homogeneous, light beige suspension;

SC well dispersible in water.

Example B.

Wettable powder

Active component - Conn. example N 37 200,0 g

Anionic surfactants - TensiofixLX Spezial5)90.0 g

Anionic surfactants - TensiofoxBCZ5)30.0 g

Carrier/filler is Kaolin to 680.0 g

The distribution of particle size: the particle Size [Ám]

x10 - 1,66

x50 - 6,54

x90 - 17,15

Appearance: homogeneous free-current light-beige powder, well-wettable and dispersible in water.

1) Product purchased from company S. A. Witko, France

2) the Product is purchased from BASF AG, Germany

3) the Product purchased from company Zeneca GmbH, Germany

4) the Product is purchased from a company in Germany

5) the Product purchased from company Omnichem.

1. Fungicidal composition comprising an active component derived triazolopyrimidine and the carrier, characterized in that, as specified derivative contains from 0.5 to 95 wt.% triazolopyrimidine compounds of General formula I

< / BR>
in which R represents soil, substituted by 1 to 3 substituents selected from halogen atoms, C1-C4-alkyl, C1-C4-halogenoalkane, C1-C4-alkoxy, C1-C4-halogenoalkane, halogenmethyl, phenyl, phenoxy and benzyloxy; fenoxaprop substituted by a halogen atom or C1-C4-alkyl; naphthyl or thienyl;

Hal - atom Cl or Br.

2. The composition according to p. 1, characterized in that the substituent R is a propyl, butyl, ethoxy, cyclopentyl, cyclohexyl, forfinal, chlorophenyl, bromophenyl, dichlorophenyl, chlorophenyl, were, propylphenyl, butylphenyl, dimetilfenil, triptoreline, methoxyphenyl, ethoxyphenyl, acid, detoxifier, trimethoxyphenyl, trifloromethyl, chlorosulfonylphenyl, biphenylyl, phenoxyphenyl, benzyloxyphenyl, fervency, chlorphenoxy, methylphenoxy, dimethylphenoxy, naphthyl or thienyl.

3. The composition according to p. 1, characterized in that triazolopyrimidine is a compound of formula I, where R is 2-chlorophenyl, and both Deputy Hal represents a chlorine atom; R represents 2-chlorophenyl, and both Deputy Hal represents a bromine atom; R represents a 4-ethoxyphenyl, and both Deputy Hal made the; R represents 2-methoxyphenyl, and both Deputy Hal represents a chlorine atom; R represents a 2-chlorosulfonylphenyl, and both Deputy Hal represents a chlorine atom; R represents a 3-triptoreline, and both Deputy Hal represents a chlorine atom; R represents a 4-isopropylphenyl, and both Deputy Hal represents a chlorine atom; R represents a 4-trifloromethyl, and both Deputy Hal represents a chlorine atom; R represents a naphthas-2-yl, and both Deputy Hal represents a chlorine atom; R represents a 4-forfinal, and both Deputy Hal represents a chlorine atom; R represents a 4-phenoxyphenyl, and both Deputy Hal represents a chlorine atom; R represents a 4-biphenyl, and both Deputy Hal represents a chlorine atom; R represents a 3,4-acid, and both Deputy Hal represents a chlorine atom; R represents a 4-benzyloxyphenyl, and both Deputy Hal represents a chlorine atom; R represents a 2-forfinal, and both Deputy Hal represents a chlorine atom; R represents a 3-forfinal, and both Deputy Hal represents a chlorine atom; R represents a 2-bromophenyl, and both Deputy Hal performance, and R represents a 2-benzyloxyphenyl, and both Deputy Hal represents a chlorine atom; R represents a 2,3-acid, and both Deputy Hal represents a chlorine atom; R represents a 3-bromophenyl, and both Deputy Hal represents a chlorine atom; R represents a naphthas-1-yl, and both Deputy Hal represents a chlorine atom; R represents a 2,3-dioxyphenyl, and both Deputy Hal represents a chlorine atom; R is a 3,4-dichlorophenyl, and both Deputy Hal represents a chlorine atom; R represents Tien-2-yl, and both Deputy Hal represents a chlorine atom; R represents Tien-3-yl, and both Deputy Hal represents a chlorine atom; R represents a 3,4,5-trimethoxyphenyl, and both Deputy Hal represents a chlorine atom; R represents a 2-were, as both Deputy Hal represents a chlorine atom; R is 3-chlorophenyl, and both Deputy Hal represents a chlorine atom; R represents a 3,4-dimetilfenil, and both Deputy Hal represents a chlorine atom; R represents cyclopentyl, and both Deputy Hal represents a chlorine atom; R represents a cyclohexyl, and both Deputy Hal represents a chlorine atom; R represents a 2-forfinal, establet a chlorine atom; R represents 4-tert.butylphenyl, and both Deputy Hal represents a chlorine atom; R represents a 2-chloro-6-forfinal, and both Deputy Hal represents a chlorine atom; R represents 4-methoxyphenyl, and both Deputy Hal represents a chlorine atom; R represents a 2-triptoreline, and both Deputy Hal represents a chlorine atom; R represents a 4-bromophenyl, and both Deputy Hal represents a bromine atom; R represents a 2-chloro-6-forfinal, and both Deputy Hal represents a bromine atom; R represents a 4-triptoreline, and both Deputy Hal represents a bromine atom; R represents a 3-forfinal, and both Deputy Hal represents a bromine atom; R represents a 2-triptoreline, and both Deputy Hal represents a bromine atom; R represents a 2-perperoglou, and both Deputy Hal represents a chlorine atom; R represents a 2-methylphenoxy, and both Deputy Hal represents a chlorine atom; R represents a 2-chlorophenoxy, and both Deputy Hal represents a chlorine atom; R represents a 2,6-dimethylphenoxy, and both Deputy Hal represents a chlorine atom; R represents the both Deputy Hal represents a chlorine atom; R represents isopropyl, and both Deputy Hal represents a chlorine atom; or R is isobut-3-yl, and both Deputy Hal represents a chlorine atom.

4. The composition according to PP.1 to 3, characterized in that it contains at least two carriers, at least one of which is a surfactant.

5. Derivatives triazolopyrimidine General formula I

< / BR>
in which R represents a C1-C6-alkyl, C1-C6-alkoxygroup, C3-C8-cycloalkyl group; fenoxaprop, replaced by a halogen atom or C1-C4-alkyl; or thienyl;

Hal - atom Cl or Br, provided that when the substituent R represents a methyl group, both group Deputy Hal are not chlorine atoms.

6. Derived triazolopyrimidine under item 5, characterized in that R represents Tien-2-yl, and both Deputy Hal represents a chlorine atom; R represents Tien-3-yl, and both Deputy Hal represents a chlorine atom; R represents cyclopentyl, and both Deputy Hal represents a chlorine atom; R represents a cyclohexyl, and both Deputy Hal represents a chlorine atom is a 2-methylphenoxy, and both Deputy Hal represents a chlorine atom; R represents a 2-chlorophenoxy, and both Deputy Hal represents a chlorine atom; R represents a 2,6-dimethylphenoxy, and both Deputy Hal represents a chlorine atom; R represents a 3-methylphenoxy, and both Deputy Hal represents a chlorine atom; R represents ethoxypropan, and both Deputy Hal represents a chlorine atom; R represents isopropyl, and both Deputy Hal represents a chlorine atom; or R is isobut-3-yl, and both Deputy Hal represents a chlorine atom.

7. The method of obtaining derivatives of triazolopyrimidine formula I defined in the PP.5 and 6, characterized in that the compound of General formula II

< / BR>
in which the substituent R takes on the values defined in the PP.5 and 6

reacts with glorieuses or brainwashin agent.

8. A method of combating fungus at a locus, characterized in that it includes processing a derivative of triazolopyrimidine, as defined in paragraph 5 or 6 or a composition according to PP.1 to 4.

9. The method according to p. 8, characterized in that under the locus refers to plants subject to or subjected to fungal infection.



 

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,5,6]-6-amino-3-azabicyclo [3.1.0] gex-3-yl)- 6-fluoro-1-(2,4-differenl)-1,4 - dihydro-4-oxo-1,8 - naphthiridine-3-carboxylic and methanesulfonic acid and its preparation" target="_blank">

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FIELD: agriculture.

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6 tbl, 4 ex

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