Derivatives of thiazole, method of production thereof and a method of combating fungi

 

(57) Abstract:

Usage: agriculture, chemical plant protection products. The inventive product f-ly I, where R is 4-chlorophenyl, 4-forfinal, 2,4-dichlorophenyl, AND WITH, NOR', compound II, R'-C-C-alkyl, cyclopropylmethyl, propen-2-yl, propyne-2-yl, benzyl, and R"is hydrogen, C-C-alkyl. Reagent 1: O= P(OR4)(OR6)CH(OR5)R, where R4, R5, R6is independently alkyl. Reagent 2: compound f-ly III in the presence of a base. Reagent 3: R ONH2or OHCH2CH(R2)OH in the presence of Lewis acid. The lesion fungi handle products in quantities of 1 kg/ha 3 C. p. F.-ly, 1 Il. The structure of the compounds f-l I, II, III:

The invention relates to certain derivatives of thiazole, method of production thereof, compositions containing such compounds and their use as fungicides.

According to the present invention features a compound of General formula l

(I)

where R 4 chlorophenyl, 4-forfinal or 2,4-dichlorophenyl,

And a group of the formula C=0, C=NOR1or

< / BR>
R1C1-C7alkyl, cyclopropylmethyl, propen-2-yl, propyl-2-yl, benzyl, 4-Chlorobenzyl, 4-bromobenzyl or 2,4-dichlorobenzyl,

R2hydrogen

R3fedoraforum (I), (the importance of groups as defined in paragraph (1), namely, that interact compounds of General formula

< / BR>
where R has the above significance, and R4, R5and R6independently represent alkyl, with a compound of the formula

(III)

where R2have the above meanings, in the presence of a base and if desired, the thus obtained compound I is subjected to interaction with the compound of General formula

R1-O-NH2(IV)

where R1defined above; or with a compound of General formula

< / BR>
where R3have the above meanings, in the presence of Lewis acid.

In addition, according to the invention provides a method of combating fungi in the lever, namely, that includes applying to the hearth fungicide-effective amount of compound I, where the effective amount of compound I is 1 kg/ha.

You must also take into account that compounds of the formula I in which a represents a group C=N-OR1that can exist in the form of various geometric isomers and compounds of formula I in which a represents a group

< / BR>
and can exist in the form of various geometrical and optical Isom the Invention also provides a method of obtaining compounds of formula I as defined above or an acid is a compound, salt or complex of the metal salt of this compound, which includes (a) reacting compounds of General formula II

(II)

in which R takes as defined above meanings and R4, R5and R6that may be the same or different, represent an alkyl group, cycloalkyl group, phenyl group or a benzene group, with a compound of General formula III

< / BR>
in which R2accepts the above specified values, in the presence of a base;

/b/, if necessary, reacting the compounds of formula I, obtained in /a/ with a compound of General formula

R1-O-NH2(IV)

in which R1accepts the above specified values, or with acid composite salt of this compound;

/c/ if necessary, reacting the compounds of formula I derived /a/ with a compound of General formula

(V)

in which R1accepts the above specified values, in the presence of a Lewis acid;

/d/ optionally reacting the compound I obtained in /a/, /b/ or /c/, with a suitable acid or by mol of the metal with the formation of acid composite salt or complex salt of a complex metal salt of the compound.

Especially preferred compound of formula II is a compound in coturoltoday Foundation, which can be used in stage (a) of the above method include lithium diisopropylamide, tertbutoxide potassium, sodium hydride and, most preferably butyl lithium.

Stage /a/ typically carried out in the presence of a solvent. Suitable solvents include dimethylformamide, dimethylsulfoxide and ethers, especially tetrahydrofuran. The reaction is usually carried out at temperatures from -100 to 100oC, and the preferred reaction temperature is from -80 to 70oC.

If a compound of General formula IV is used in the stage of /b/, it is preferable that the connection was received on the spot. If you use acid composite salt of the compounds of General formula IV, the method is conveniently carried out in the presence of a base such as sodium acetate.

Stage /b/ is conveniently carried out in the presence of a solvent. Suitable solvents include dimethylformamide, dimethylsulfoxide, ethers such as tetrahydrofuran, aromatic compounds and alcohols, especially methanol and ethanol. The reaction is suitably carried out at a temperature of 0-100oC, and the preferred temperature range is from 15 to 80oC.

In stage /c/ preferably cicloturista acid, such as a pair of toluensulfonate or methansulfonate.

Stage /c/ can be carried out in the presence of an inert solvent. Suitable solvents include aromatic compounds such as xylene. Alternatively, an excess of the compounds of formula V may serve as a solvent. The reaction is conveniently carried out at a temperature of from 0 to 170oC, and the preferred reaction temperature is from 15 to 150oC.

The compounds of formula II can be obtained according to the method described by D. Burkhous, H. Zimmer, Synthesis 1984, 330. The compounds of formula III in which R2is a different group than the alkyl group can be obtained by the reaction of thiourea with 3-bromo-1,3-propandiol and then by the reaction of 2-aminothiazole carboxaldehyde hydrobromide thus obtained, with amenities. The compounds of formula III in which R2means alkyl group, can be obtained by reaction of the corresponding allylthiourea with 2-bromo-1,3-propandiol and similar way. 2-bromo-1,3-PROPANEDIOL can be obtained according to the method described in S. Trofimenko J. Org. Chem. 1963, 28, 3243.

The compounds of formula IV and V are known compounds or can be obtained by methods similar to known what some of the compounds of formula I, it has been found that show evaporative activity. According to this, the invention further provides a fungicidal composition which comprises a carrier and, as active ingredient, a compound of formula I or acid-salt compound, or a complex metal salt of this compound, as defined above. The method of obtaining such a composition is also offered, and the method comprises bringing the compound of formula I as defined above, or an acid-compound salts or complex metal salt of this compound in communication with at least one carrier. Such a composition may contain a single compound or a mixture of several compounds of the present invention. It is also envisaged that different isomers or mixtures of isomers can be different levels or activity spectrum and, thus, the composition can include individual isomers or mixture of isomers.

Compositions according to the invention preferably contain from 0.5 to 95 weight. the active ingredient.

A carrier in a composition according to the invention is any material with which the active ingredient is formed to facilitate application to the treatment site, which may be, for example, plant, behold the or liquid, including material, which is usually in gaseous form, but when compressed, forms a liquid, and can be used any of the carriers normally used for molding fungicidal compositions.

Suitable solid carriers include natural and synthetic clays and silicates, for example, natural silicates, such as hard-shelled land; magnesium silicates, for example, talc; magnesium silicates, for example, attapulgite and vermiculite; silicates, kaolinites, montmorillonite and micas; calcium carbonate; calcium sulphate; ammonium sulphate; synthetic hydrated oxides of silicon and synthetic calcium silicates or aluminum; elements, for example, carbon and sulfur; natural and synthetic resins; for example, coumarone resins, polyvinyl chloride and polymers and copolymers of styrene; solid polihlorvinila; bitumen; waxes, for example, beeswax, paraffin wax, and chlorinated mineral waxes; and solid fertilizers, such as superphosphate.

Suitable liquid carriers include water, alcohols, such as isopropanol and glycols; ketones, for example acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ethers; aromatic and analiticheskie hydrocarbons such as benzene, Tolimir, kerosene and light mineral oils; chlorinated hydrocarbons such as carbon tetrachloride, perchloroethylene and trichloroethane. Often mixtures of different liquids.

Fungicidal compositions are often formed and transported in a concentrated form, which is subsequently diluted before use. The presence of small amounts of media, which is a surface-active agent, facilitates this process of dilution. Thus, preferably at least one carrier in a composition according to the invention is a surface-active agent. For example, the composition may contain at least two media, one of which at least the surface-active agent.

Surface-active agent may be an emulsifying agent, dispersing agent or wetting agent; it may be nonionic or ionic. Examples of suitable surface active agents include salts of sodium or calcium polyacrylic acids and lignin sulphonic acids; the condensation products of fatty acids or aliphatic amines or amides containing at least 12 carbon atoms in the molecule with

with ethylene oxide and/or propylene oxide; complex is nexicom and/or propylene oxide; condensation products of fatty alcohol or alkyl phenols, for example, para-op or para-ochiltree, with ethylene oxide and/or propylene oxide; sulfates or sulfonates of these condensation products, salts of alkaline or alkaline earth metals, preferably sodium salts, esters of sulfuric or sulfonic acids containing at least 10 carbon atoms in the molecule, for example, sodium lauryl sulphate, sodium secondary alkyl sulfate, sodium salt from sulphonated castor oil, and sodium alkylarylsulfonate, such as dodecylbenzene the sulfonates; and polymers of ethylene oxide and copolymers of ethylene oxide and propylene oxide.

Compositions of the invention can be molded in the form of wettable powders, Farrukh Dustov, granules, solutions, emulsion concentrates, emulsions, suspension concentrates and aerosols. Wettable powders usually contain 25, 50 or 75 weight. the active ingredient and usually contain in addition to solid inert carrier 3-10 weight. dispersing agent and, where necessary, 0-10 weight. stabilizer /stabilizer/ and/or other additives, such as wetting agents and thickeners. Dusty usually shaped in the form of gustovich concentrates having the same composition to the media receiving the composition, usually containing 0.5-10 weight. the active ingredient.

Granules usually get the sizes of 10-100 mesh. (1,676-0,152 mm), and can be obtained using the methods of agglomerating or impregnating. Typically, the granules contain from 0.5 to 75 weight. the active ingredient and 0-10 weight. additives such as stabilizers, surface-active agents, modifiers slow allocation and binding agents. The so-called "dry bulk powders are composed of relatively small granules having a relatively high concentration of the active ingredient. Emulsion concentrates usually contain, in addition to the solvent, if necessary, co-solvent, 1-50 weight. the amount of active ingredient, 2-20 W/V emulsifiers and 0-20 weight/volume of other additives such as stabilizers, wetting agents and corrosion inhibitors. Suspension concentrates are usually compendious thus, to obtain a stable resedimented products capable of transfusion, and usually contain 10-75 weight. the active ingredient, 0.5 to 15 weight. dispersing agent, 0.1 to 10 weight. a suspending agent, such as protective colloids and thixotropic agents, 0-10 weight. other additives, such as providing agents, corrosion inhibitors, stabilizers, which have insoluble; certain organic solids or inorganic salts may be dissolved in the composition to prevent sedimentation or as antifreeze for the water.

Aqueous dispersions and emulsions, for example compositions obtained by diluting wettable powders or concentrates according to the invention with water, such are within the scope of the claims of the invention. These emulsions can be of the type "water in oil" or "oil-in-water, and may have a thickness that is similar to the consistency of a "mayonnaise".

The composition of the invention may also contain other ingredients such as other composition having herbicide, insecticide or fungicide properties.

Of particular interest in enhancing the duration of protective activity of the compounds of the present invention is to use a carrier that will provide a slow allocation of fungicidal compounds into the environment of plants that should be protected. Such compositions with a slow selection can, for example, be introduced into the soil near the roots of vines, or may include adhesive component, able to apply the compound directly to the post grape is the soup of the formula I as defined above or an acid-compound salts or complex metal salt of this compound or composition as defined above, and the way to fight flexible in the lesion, which includes treatment center that can be for example plants subjected or exposed to fungus, seeds of such plants or the medium in which such plants are grown or to be grown, such a compound or composition.

The invention is widely applicable in the protection of agricultural crops against the impact of a fungus.

Typical crops which may be protected include, grapes, cereals, such as wheat and barley, rice and tomatoes. The duration of protection is usually dependent on the selected connection, as well as many external factors such as climate, whose influence is usually facilitates the use of a suitable composition.

Example 1. Getting 1-/2,4-dichlorophenyl/-2-/5-thiazole/ethanol /R=2,4-dichlorophenyl, And C=0, R2=hydrogen/.

/i/ Receiving 5-thiazolecarboxamide.

The thiourea /33, g, of 0.44 mol/ added to a solution of 2-bromo-1,3-propandiol /66 g of 0.44 mol/ acetone /1 l/ and the resulting mixture was stirred thoroughly under boiling under reflux for 1 h After cooling to room temperature the solid is solid substance with a melting point 126oC.

A solution of 2-aminotetraline hydrobromide /35 g, has 0.168 mol/ methanol was neutralized with sodium methoxide /9 g, has 0.168 mol/. Then the methanol is evaporated under reduced pressure until a dry residue, which was suspended in tetrahydrofuran /200 ml and was slowly added to boiling under reflux the solution amylnitrate /31 g/ tetrahydrofuran /300 ml/. The resulting mixture was boiled under reflux for 1 h, cooled, filtered, and then concentrated under reduced pressure. To the residue was added diethyl ether /400 ml and the mixture then was stirred for one hour, filtered, and concentrated. Then the residue was chromatographically on silica gel using a mixture of 2:1 petroleum ether: diethyl ether as eluant obtaining 5-thiazolecarboxamide /4.4 g/ in the form of a yellow solid with a melting point 15oC.

/ii/ Receiving 1-/2,4-dichlorophenyl/-2-/5-thiazolyl/ethanol.

Butyl lithium /2.5 M, 14 ml in hexane was added dropwise to a solution of diethyl - /2,4-dichlorophenyl/methoxymethyl phosphonate /12.8 g, 39 mmol/ tetrahydrofuran /150 ml/ -78oC in nitrogen atmosphere. The resulting intensely red solution was stirred at dehydrogenase /50 ml/. After soaking for 1 h at a temperature of -78oC the reaction mixture was allowed to warm to room temperature at which the mixture was treated with water and then acidified with concentrated sulfuric acid /35 ml and boiled under reflux for 20 hours After cooling, the tetrahydrofuran is evaporated and the aqueous residue was neutralized with sodium carbonate and then extracted with ethyl acetate /2 x 200 ml/. The combined organic extract was washed with a saturated solution of sodium chloride, dried and concentrated. Then the residue was chromatographically on silica gel using a mixture of 7:3 petroleum ether: ethyl acetate as eluant obtaining 1-/2,4-dichlorophenyl/-2-/5-thiazolyl/ethanone /5.75 g/ in the form of a light yellow substance with a melting point 75-77oC.

Analysis:

Calculated: FROM 48.5, N 2,6, N 5,1%

Found: FROM 47.9, N 2,6, N 5,0%

Example 2. Getting 1-/2,4-dichlorophenyl/-2-/5-thiazolyl/ethanol 0-atraxia. /R=2,4-dichlorophenyl; AND C=N-OR1; R1ethyl: R2hydrogen/.

A mixture of 1-/2,4-dichlorophenyl/-2-/5-thiazolyl/ethanol /1.1 g, 4 mmole/ obtained in example 1, sodium acetate /1.64 g, 20 mmol/ and 0-ethylhydroxylamine hydrochloride /1,95 n, 20 mmol/ boiled under reflux in the/ to the reaction mixture and then concentrated under reduced pressure. The aqueous residue was podslushivaet sodium carbonate and then extracted with ethyl acetate /h ml/. The combined organic extracts were then washed with a saturated solution of sodium chloride, dried and concentrated. Chromatography of the residue on silica gel using a mixture of 4:1 petroleum ether /40-60/:ethyl acetate as eluant has resulted in the quality of the connection And E-isomer /0.88 g/ and as a connection in the Z-isomer /0.20 g/ 1-/2,4-dichlorophenyl/-2-/5-thiazolyl/ethanol in the form of butter.

Analysis of E/Z mixture

Calculated: 49,5, N 3,8, N 8,8%

Found: 51,0, N 4,3, N 8,4%

Example 3. Getting 2-/2,4-dichlorophenyl/-2-/-thiazole-5-ylmethyl/-1,3-dioxolane /R is 2,4-dichlorophenyl; R1=hydrogen, R2=hydrogen,

< / BR>
A mixture of 1-/2,4-dichlorophenyl/-2-/5-thiazolyl/ethanone /1,49 g, 5.4 mmole/ obtained in example 1 and trimethylchlorosilane /2,8 ml/ ethane-1,2-diole -25 ml/ was stirred at 90oC for 4 h and then cooled at room temperature. Then the reaction mixture was poured into sodium bicarbonate solution, extracted with ethyl acetate, washed with water and dried over magnesium sulfate. Evaporation of the solvent under reduced pressure resulted in a dark brown oil and flash chromatography of this oil on silica gel in to the Nile/-2-/Tasol-5-ylmethyl/-1,3-dioxolane /0.64 g/ in the form of a yellow oil.

Analysis.

Calculated: 49,5, N 3,8, N 4,4%

Found: 51,2, N 4,3, N 4,3%

Example 4. Getting 2-/2,4-dichlorophenyl/-2-/thiazole-5-ylmethyl/-4-methyl-1,3-dioxolane

/R is 2,4-dichlorophenyl, R1=methyl, R2=hydrogen,

A mixture of 1-/2,4-dichlorophenyl/-2-/4% thiazolyl/ethanone, /1.5 g, 11 mmol/ obtained in example 1, trimethylchlorosilane /6 ml/ trimethylsilane /2 ml/ propane-1,2-diole was stirred at 110oC for 4 h and then cooled to room temperature. The reaction mixture was then poured into sodium bicarbonate solution, extracted with ethyl acetate, washed with water and dried over magnesium sulfate. Evaporation of the solvent under reduced pressure resulted in a dark brown oil and flash chromatography of this oil on a column of silica gel using a mixture of 5:95 /volume/ diethyl ether: dichloromethane as eluant led to a 2-/2,4-dichlorophenyl/-2-/thiazole-5'-ylmethyl/-4-methyl-1,3-dioxolane /1,89 g/ in the form of a mixture of isomers. Subsequent flash chromatography of the product in the column of silica gel using a mixture of 1:9 /volume/ ethyl acetate: petroleum ether /60-80/ as eluent resulted in two enantiomeric pairs of the target product as a sample And /2R, 4R/ /2S, 4S/ 0,49 g and sample Example 5.

Getting 2-/4-forfinal/-2-/thiazole-5-ylmethyl/-4-methyl-1,3-dioxolane.

/R 4-forfinal, R1=methyl, R2=hydrogen,

A mixture of 1-/4-forfinal/-2-/5-thiazolyl/ethanone /0.75 g, 3.3 mmole/, obtained by the method similar to the method of example 1, propane-1,2-diol /2 ml/ methansulfonate /0.5 ml/ xylene /30 ml/ was stirred while boiling under reflux in nitrogen atmosphere for 2 h using a device Devn and Stork and then cooled to room temperature. Then the reaction mixture was poured into ice water, extracted with ethyl acetate and dried over magnesium sulfate. Evaporation of the solvent under reduced pressure yielded a dark brown oil and flash chromatography of this oil on a column of silica gel using a mixture of 2:8 /volume/ ethyl acetate:petroleum ether 60-80 resulted in the receipt of two enantiomeric pairs of 2-/4-forfinal/-2-/thiazole-5-methyl-1,3-dioxolane as a sample A /2R, 4R/ /2S, 4S/ 0.17 g and sample /2R, 4S/ /2S, 4R/ 0.11 g in the form of oils.

Analysis: /mixture and/

Calculated: 60,2, N, 5,0, N 5,0%

Found: 61,5, N 5,9, N, 4,6%

Examples 6-35. According to the methods described in examples 1-5, were obtained the following compounds according to the invention as it is presented in detail in table. 1. In table. 1 with the AIA for the compounds of examples 6-35 presented in table. 1A.

Example 36. The fungicidal activity of the compounds of the invention was investigated using the following tests.

/a/ Antispammeta activity against grape disease / (Plasmopara viticola, Pva).

The test is in direct application anticorrelate using spray on the foliage. The lower surface of the leaves of grape plants/ CV Cabernet Sauvingnon/ inoculable by spraying aqueous suspensions containing 104the zoosporangium inside host/ml for 2 days before treatment with test compound. Inoculated plants were maintained 24 h in conditions of high humidity, then 24 h at ambient temperature and humidity in the greenhouse. Infected leaves were sprayed with their lower sides with a solution of the active substance in a mixture of 1:1 water/acetone containing 0.04% of "TWEEN"20" /brand surfactants of the complex ester of polyoxyethylene and sorbent Spraying was performed using a spray bottle to apply a dose of 1 kg/ha After spraying, the plants were returned to normal greenhouse conditions for 96 h and then transferred in conditions of high humidity and within 24 h for induction of sporulation before the evaluation. The assessment is based on the percentage of the surface of the sheet against grape peronospora /Plasmopara viticola. Pvp/.

The test is aimed at direct protection to the plants by spraying the leaves. The lower surfaces of leaves of whole vine plants /CV Cabernet Sanvignon/ were sprayed with the test compound at a dose of 1 kg of active substance per hectare using sprinklers as described in /a/, and after a further 24 h under normal conditions of greenhouses lower leaf surface was inoculable by spraying an aqueous solution containing 104the zoosporangium inside host/ml Inoculated plants 24 h were kept in high humidity conditions, 5 days in normal greenhouse and then returned 24 h in conditions of high humidity. The evaluation was performed in the calculation of the percentage of leaf area covered with sporulation compared with control leaves.

/c/ Immediate protective activity against grape gray rot /Botrytis cinerea, Bcp/.

The test is a direct protection by spraying foliage. The bottom surface separated grape leaf /cv Cabernet Sanvignon/ sprayed test compound at a dose of 1 kg/ha with spray as in /a/. After 24 h after spraying the leaves were inoculable drops of water suspension containing 105conidia/ml After 5 days of nagode is here against leaf spot of wheat /Zeptosphaeria nodorum, Zn/.

The test is directly therapeutic using leaf spraying. Leaves of wheat plants /cv Mardler/ at the stage of the first sheet was inoculable by spraying aqueous suspensions containing 1x106spores/ml Inoculated plants were kept in high humidity conditions for 24 h before processing.

The plants were sprayed with a solution of the test compounds at a dose of 1 kg of active substance per hectare using sprinklers as described in /a/. After drying, the plants contained 6-8 days at 20-25oC and average humidity, after which it was assessed, the assessment was based on the density of lesions per leaf compared with the leaves of the control plants.

/e/ Activity against powdery mildew of barley /Erysiphe graminis f. sp. hordei, Eg/.

The test is a direct test using a spraying foliage. The leaves of the sprouts of barley /cv Golden Promise/ inoculable pollination mildew, conidia the day before processing the test connection. Inoculated plants were kept in over night in the greenhouse at room temperature and humidity before processing. Plants were sprayed with the test compound at a dose of 1 kg of active substance on GE is UP>C and average humidity for 7 days, and then evaluated. The assessment was based on the percentage of leaf area covered with sporulation compared with the leaves of the control plants.

/f/ Activity against brown rust of wheat /Puccinia recondita. Pr/.

The test is a direct test using a spraying foliage. Wheat germ /cv Brigand/ brought to stage 1-1,5 sheet. Then the plants were sprayed with the test compound at a dose of 1 kg/ha with the use of sprinklers as described in /a/. Compound was used in the form of solutions or suspensions in a mixture of acetone and water /50:50 by volume/ containing 0.04% of a surfactant /"WEEN-20" - brand/.

After 18-24 h after treatment, the shoots were inoculable by spraying plants in all places aqueous spore suspension containing 105dispute/Il. Within 18 h after inoculation the plants were kept in high humidity conditions at a temperature of 20-22oC. the plants were kept in greenhouse conditions, i.e. in terms of the average relative humidity and at a temperature of 20oC.

The lesion was assessed 10 days after inoculation on the percentage of plants covered tularosa rice sheet /Pyricularia oryzae, Po/.

The test is a direct therapeutic trial using spraying foliage. The leaves of sprouts risk /about 30 sprouts in a pot/ sprayed with an aqueous suspension containing 105spores/ml for 20-24 h before processing the test connection. Inoculated plants were maintained during the night with high humidity and then allowed to be dried before spraying the test compound at a dose of 1 kg of active substance /ha with spray as described in /a/. After treatment, plants were kept in rice the camera at 25-30oWith high humidity. Evaluation was made after 4-5 days after treatment and assessed the density of necrotic lesions on the leaf compared with the control plants.

/h/ Activity against leaf spot of tomatoes /Alternaria Solani, As./

This test assess the contact preventive activity of the tested compounds, applied in the form of a spray of foliage.

Sprouts tomato /cv Outdoor Gure/ grew to a stage at which reveals the second true leaf. Plants were treated with the use of sprinklers as described in /a/. Compound was used in the form of solutions or suspensions in a mixture of acetone and water /50: the Le handle sprouts were inoculable spraying the upper surface of the leaves with a suspension of A. solani conidia containing 104spores/ml Within 3 days after inoculation plants are kept moist in the chamber of the greenhouse at 100% relative humidity and 21oC. the plants were kept in humid conditions, but not close to saturation.

The lesion was evaluated at 7 days after insulinopenia density and distribution of lesions.

/i/ Activity against cercosporella wheat in vitro /Pseudocercosporella herpotrichoides. PhI/.

This test evaluated the in vitro activity of compounds against fungi causing cercosporella wheat.

The test compound dissolved or suspended in acetone and add to the melted half the agar potato dextrose with getting 100 ppm connection and 3.5% acetone. After solidification of the agar plates were inoculable plug with a diameter of 6 mm of a mixture of agar/micelles, taken from the culture of P. herpotrichoides at the age of 14 days.

Plates were incubated at 20oC for 12 days and were evaluated by the radial growth of the inoculated blank.

/i/ Activity against Fusarium in vitro /Fusarium species, FsI/.

This test evaluated the in vitro activity of compounds against Fusarium species, which causes rotting of the trunk is well the agar potato dextrose to obtain a final concentration of 100 ppm of the compound and 3.5% acetone. After solidification of the agar plates were inoculable plugs with a diameter of 6 mm from the agar and micelles, taken from the culture of Fusarium sp. at the age of 7 days.

Plates were incubated at 20oC for 5 days and assessed the radial growth of the stub.

The damage degree of control in all the above tests were expressed as a ratio compared with either untreated control or control, sprayed only with diluent according to the following criteria:

0 less than 50% of affected control

1 about 50-80% of affected control

2 more than 80% of affected control

The results of these tests are presented in table. 2: /abbreviation fungi above in paras. /a/-/j/.

Example 37. Evaporative activity against powdery mildew of barley /Erysiphe graminis, Eg/. Barley grass /cv Golden Promise/ grew to the stage 1+sheet peas 7 cm and was inoculable mildew conidia one day before processing the test connection. Then the plants were sprayed with a solution of the test compound in a mixture of 1:1 water:acetone containing 0.04% of "WEEN 20"/ brand surfactant complex ester of polyoxyethylene and sorbitan /dose application of 1 kg/ha with a soft brush. Then ODA is found Plexiglas wall 60 cm2. After 7 days on all plants was estimated percentage defeat the disease. High levels of destruction on popricani plants within the walls, similar levels of disease control on plants outside the walls show low evaporative activity, while significantly lower lesion level on popricani plants within the walls is a good proof evaporative activity.

Results.

shows a pot plant within the walls, with X% of the damaged coating.

The pot labeled "0" in the upper right (see drawing) sprayed with the compound of example 13A. Low levels lesions show that the compound of example 13A shows evaporative activity.

In order to show the advantages of the claimed compounds was compared with compounds similar in structure and activity, described in US 4112107.

Specifically, it was tested 2-bromo-5-nitrothiazol using the method of example 36 /d/ and /e/ of this application.

As can be seen from the following data, the known connection is inactive against Leptosphaedria nodorum /Ln/ and Erysiphe graminis /Eg/, whereas all tested in this application connections appear the deposits of 2-bromo-5-nitrothiazole

TTT

1. Derivatives of thiazole of General formula

< / BR>
where R is 4-chlorophenyl, 4-forfinal or 2,4-dichlorophenyl;

And a group of the formula-Oh, -NOR With1or

< / BR>
R1C1-C7-alkyl, cyclopropylmethyl, propen-2-yl, propyne-2-yl, benzyl, 4-Chlorobenzyl, 4-bromobenzyl or 2,4-dichlorobenzyl;

R2hydrogen;

R3hydrogen or C1-C3-alkyl.

2. The method of obtaining derivatives of thiazole under item 1, characterized in that interact compounds of General formula

< / BR>
where R has the above meanings;

R4, R5and R6independently represent alkyl,

with the compound of the formula

< / BR>
where R2has the specified value,

in the presence of a base, and if desired, the thus obtained compound is subjected to interaction with the compound of General formula

R1O NH2,

where R1has the specified values,

or with a compound of General formula

< / BR>
where R3has the specified values,

in the presence of Lewis acid.

3. A method of combating fungi in the lesion by processing its derivatives of thiazole, characterized in that as a derivative of thiazole is used to connect the

 

Same patents:

The invention relates to thiazole derivative, method for their production and their use as fungicides

The invention relates to methods of producing derivatives of thiazolidinone formula II:

in which R1represents a C2-C6alkenyl,2-C6quinil or group (CH2)n-Sin which n is an integer in the range 0-3, including extreme values of the interval;

R2represents hydrogen, C1-C6alkyl, C1-C6alkoxy,

WITH2-C6alkenyl,2-C6quinil,1-C4-alkyl-O-

-CC1-Calkyl or -CH-Swhere n is an integer in the range 0-3, including both extreme values;

R3represents hydrogen or C1-C6alkyl;

R4and R5represents hydrogen or together form a bond;

R6and R7each represents hydrogen and the another group-OH or SCH3;

X represents a group ofwhere m is 0,1 or 2, and

Q represents NR8where R8represents hydrogen, C1-C6alkyl, C2-C6alkenyl,3-C8cycloalkyl, SO2CH3or -(CH2)n-Y; where n is an integer in the range 0-3, including both extreme values, and

Y represents cyano, OR9, -R10< / BR>
-NR11TO12S-(C1WITH4) alkyl or a group

O-C1-C4alkyl where R9represents hydrogen, C1-C4alkyl or the group --C1-C4-alkyl

R10represents a C1-C4alkyl, C1-C4alkoxy, or-NH2< / BR>
R11and R12independently of one another represent hydrogen, C2-C6alkenyl,2-C6quinil,1-C6alkyl, (CH2)qOH, -(CH2)q-N(C1-C4alkyl)2,

-(CH2)q-S(C1-C4alkyl) or

-(CH2)11and R12together form morpholino, piperidinyl, piperazinilnom or N-methyl-piperazinilnom ring, or its pharmaceutically acceptable salts, characterized in that exercise: the reaction of the compound of the formula

HO-R3with the compound of the formula

in which R1, R2, R3and X have the above values, Q represents N-R8(where R8has the specified values), and R6and R7together form a group S, with the aim of obtaining the compounds of formula

in which R1, R2, R3, R6, R7, X and Q have the above meanings;

(a) with subsequent optional recovery of the compounds of formula II in which R6and R7together form a group S in order to obtain the compound of formula II in which R6and R7represents hydrogen;

(C) recovering the compounds of formula II in which R4and R5together form a connection with the purpose of obtaining compounds of formula II in which R4and R5before the form a bond, and R6and R7together form a group=S to obtain the compounds of formula II in which R4, R5, R6and R7represent hydrogen;

(d) alkylation of compounds of formula II in which R3represents hydrogen with formation of compounds of formula II in which R8represents a C1-C6alkyl, C2-C6alkenyl,3-C6cycloalkyl or -(CH2)n-Y (where n is an integer in the range 0-3, including extreme values, and Y represents cyano, OR9,-SH, -S(C1-C4alkyl)-NR11R12or

O-C1-C4alkyl, where R9,R11and R12have the listed meanings: (e) atilirovanie the compounds of formula II in which R8represents a hydrogen in order to obtain the compounds of formula II in which R8represents -(CH2)n-Y, where n is an integer in the range 0-3, including both extreme values of the interval, and Y represents -R10where R10has the specified values;

(f) oxidation of compounds of formula II, Kotor is Lew obtain the compounds of formula II, in which X represents a group -m is 1;

(K) the recovery of the compounds of formula II in which R3represents a group -(CH2)n-Y where n has values in the range 0-3, including extreme values of the interval, Y is a OR9where R9represents a group --C1-C4alkyl order to obtain the compounds of formula II in which R8represents a group -(CH2)n-Y where n is 0-3, including both extreme values, and Y is a OR9where R9represents hydrogen;

(l) the reaction of compounds of formula II in which R8represents a group -(CH2)n-Y, where n is 0-3, including both extreme values of the interval, Y is-OR9where R9represents hydrogen, tosylchloramide, with the aim of obtaining the compounds of formula II in which R8represents -(CH2)n-Y, where n is 0-3, including both extreme values of the interval, and Y is a OR9where R9is tosyl;

(m) the reaction of compounds of formula is I, and Y is-OR9where R9toil, with an amine of the formula HNR11R12(where R11and R12have the specified values), with the aim of obtaining the compounds of formula II in which R8represents a group -(CH2)n-Y, where n is 0-3, including both extreme values, and Y represents NR11, R12;

(n) heating the compounds of formula II in which R8represents -(CH2)n-Y, and Y represents NR11R12(R11, R12not hydrogen) in a mixture of ethanol/water in the presence of the catalyst in order to obtain the compounds of formula II in which R8represents -(CH2)n-Y, Y represents NR11R12where R11, R12one hydrogen and the other is not a hydrogen

The invention relates to new fungicidal pyrotechnic composition which may find application in agriculture, food and light industry

The invention relates to synergistic combinations of the known fungicidal active ingredients and their use as plant protection

The invention relates to thiazole derivative, method for their production and their use as fungicides

The invention relates to new aminoven derivatives, processes for their production and insecticide containing as selective compounds listed derivatives

FIELD: organic chemistry, pesticides, agriculture.

SUBSTANCE: invention relates to compounds that elicit high pesticide activity and can be used in control of pests of domestic and agricultural animals. Indicated compounds show the formula (I):

wherein R1 means halogen atom, (C1-C6)-halogenalkyl; R2 means hydrogen atom (H), (C1-C6)-alkyl, (C1-C6)-alkylene-phenyl; X1 means nitrogen atom (N); X2 means group C(CN); X3 means oxygen atom (O); Q means CH; R3 and R4 mean independently of one another hydrogen atom (H) or in common with carbon atom with which they are bound form (C3-C7)-cycloalkyl ring; R5 means a substitute taken among group including (C1-C6)-halogenalkyl, halogen atom being if m above 1 then substitutes R5 can be similar or different; m = 1, 2 or 3; n = 0 or 1. Also, invention describes a method for their preparing and method for control of pests.

EFFECT: valuable pesticide properties of compounds.

7 cl, 3 tbl, 14 ex

FIELD: agriculture.

SUBSTANCE: invention relates to composition for seed pickling in form of water suspension concentrate containing thebuconazole and thiabendazole in ratio from 20:1 to 1:20 as active ingredients, nonionic and anionic surfactants, thickener, antifreeze, antifoaming agent, conserving agent, pigment, mineral or vegetable oil, lubricating agent, and water. Preparation of present invention has long shelf-life, freeze resistance, heat aging stability, beneficial effect on plant germination and harvest, and high biological activity. Method for controlling of plant diseases also is disclosed.

EFFECT: seed pickling composition of improved quality.

6 cl, 6 tbl, 5 ex

FIELD: agriculture, organic chemistry.

SUBSTANCE: invention relates to agent for controlling of plant pathogen fungi containing compound of general formula I as active ingredient, wherein X represents =N-; E represents NO2 or CN; R representsthiazolulmethyl or pyridylmethyl substituted with halogen; A represents hydrogen; Z represents C1-C4-alkylamino group; or A and Z together with atoms bonded thereon form thiazolidine, imidazolidine, hexahydro-1,3,5-triazine, N2- and N5-substituted with two C1-C4-alkyl in alkyl group, 6-membered saturated heterocycle fragment including additionally oxygen and N-(C1-C4)alkyl heterogroup; and fungicide compound selected from group containing cyproconazole, triadimenol, methalaxide, azoxistrobin, kresoximmethyl, etc., in weight ratio compound of formula I/fungicidal agent of 1:(0.1-10). Also disclosed is insecticide agent containing compound of formula I and compound selected from group containing cyproconazole, azoxistrobin, kresoximmethyl, biterthanol, tiram, methalaxide, etc. in ratio of 1:(0.1-10).

EFFECT: enhanced assortment of agents for controlling of plant pathogen fungi and agents for insect controlling.

4 cl, 15 tbl, 15 ex

FIELD: organic chemistry, insecticides.

SUBSTANCE: invention relates to an insecticide-acaricide agent comprising a mixture of compound of the formula (I): wherein X means halogen atom, (C1-C4)-alkyl, (C1-C4)-alkoxyl; W, Y and Z mean independently of one another hydrogen atom (H), halogen atom, (C1-C4)-alkyl, (C1-C4)-alkoxyl; A means H, (C1-C6)-alkyl; B means H, methyl or ethyl; A and B in common with carbon atom to which they are bound form saturated unsubstituted (C3-C6)-ring or substituted with (C1-C4)-alkoxy-group; D means H, (C1-C6)-alkyl; G means H or one of the following groups: (b) or (c) wherein L means oxygen atom (O); M means O; R1 means (C1-C10)-alkyl, (C3-C6)-cycloalkyl that if necessary can comprise one nitrogen atom (N) or O; R2 means (C1-C10)-alkyl and agonist, respectively, antagonist of nicotine acetylcholine receptors chosen from the group comprising compounds of formulas: (IIa) (IIe) (IIg) (IIh) (IIi) (IIk) (IIl) and (IIm) taken in synergetically effective ratio.

EFFECT: valuable biological properties of substances.

6 cl, 22 tbl, 6 ex

FIELD: herbicides, agriculture.

SUBSTANCE: invention describes a herbicide agent with selective effect comprising a combination of biologically active substances and involving the following components: (a) compound of the formula (I) given in the invention description wherein Q1 means oxygen atom (O); Q2 means O; R1 means alkyl with number of carbon atoms from 1 to 6; R2 means alkyl with number of carbon atoms from 1 to 6; R3 means alkyl with number of carbon atoms from 1 to 6 substituted if necessary with (C1-C4)-alkoxyl or alkoxy-group with number of carbon atoms from 1 to 6; R4 means alkyl with number of carbon atoms from 1 to 6 or cycloalkyl with number of carbon atoms from 3 to 6, and salts of compounds of the formula (I) also, and (b) compound improving compatibility with crop plants and chosen from compounds of the following group: AD-67, cloquintocet-methyl, dichloramide, phenchlorazol-ethyl, flurazol, furylazol, isoxadiphen-ethyl, mefenpir-diethyl, MON-7400, compound of the formula (IId) given in the invention description, compound of the formula (IIe) given in the invention description wherein per 1 weight part of compound of the formula (I) or its salt is taken from 0.4 to 200 weight parts of compound of the group (b). Proposed herbicide agent prevents damage of crop plats and can be used for selective control against weeds in cultures of useful plants, for example, cereals and maize.

EFFECT: valuable properties of herbicide agent.

7 cl, 36 tbl, 3 ex

FIELD: chemistry.

SUBSTANCE: present invention pertains to a malononitrile compound with formula (I): where one of X1, X2, X3 and X4 stands for CR100, where R100 is a group with formula (II) each three of the other X1, X2, X3 and X4 is nitrogen or CR5, under the condition that, from one to three of X1, X2, X3 and X4 stands for nitrogen, Z is oxygen, sulphur or NR6. The malononitrile compound can be used a pesticide in agriculture.

EFFECT: obtaining a new pest control compound and its use as an active ingredient of a pesticide composition.

18 cl, 180 ex

FIELD: chemistry.

SUBSTANCE: described are compounds of formula (I), in which Ar represents group of formula (A), (B1), (B2) or (C), or (D1), or (D2); R1, R2, R3, R4, R5, n, A1, A2, A3, A4, A5, Ka, Kb, L, M, V, W, X, Y, Z havevalues, determined in i.1 of invention formula, fungicide composition and method of combatting phytopathogenic fungi or their elimination, using compounds of formula (I).

EFFECT: high fungicide activity.

22 cl, 142 tbl, 34 ex

FIELD: agriculture.

SUBSTANCE: composition preventing plant diseases including components I and II as active ingredients is described. Component I is (RS)-N-[2-(1,3-dimethylbutyl)thiophene-3-yl]-1-methyl-3-trifluoromethyl-1H-pyrazol-4-carboxamides. Component II is selected from tetrakonazol, flutriafol, imibenkonazol, triadimefon, simekonazol, oxpokonazol fumarate, protiokonazol, bupirimate, spyroxamine, metiram, dodine, anilazine, chlozolinate, oxicarboxine, ethaboxam, iprovalikarb, pirazophos, phtorimide, diflumetorim, fenhexamide, famoxadone, fenamidone, ciazofamide, zoxamide, ciflufenamide, boskalid, isopropyl bentyavalikarb, pikoxistrobine, piraklostrobine, fluoxastrobine or dimoxistrobine. Also, the method preventing plant disease is described.

EFFECT: composition has synergistic effect which is not expected for each separate components, is able to significant increase of preventive effect against different phytopathogens with lower quantity of chemicals and do not invoke phytotoxic lesion.

2 cl, 9 tbl, 6 ex

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