Ethynylbenzoate

 

(57) Abstract:

Connection ethynylbenzoate formula given in the description of the invention, act as pesticides.R is chosen from the above in the description of the formula, R1selected from hydrogen, halogen, lower alkyl, lower guloudajie and fenretinide, R2selected from halogen, lower alkenyl, low allylthiourea, lower haloalkyl, guidancearticle, lower alkoxycarbonyl, (lower alkoxycarbonyl-lower alkenyl)group, phenyl, 2-tanila, and methyltin-2-yl, R3selected from alkyl, lower trialkylsilyl, lower haloalkyl, oxyalkyl, alkylcarboxylic, methylene-2-yl, 2-tanila and bestien-2-yl, R4selected from hydrogen, halogen, lower alkyl, lower haloalkyl, low alkoxygroup, niche of haloalkylthio, lower alkoxycarbonyl, amino and alkylcarboxylic. 5 C.p. f-crystals, 6 PL.

The invention relates to light-sensitive pesticides, specifically to some ethynylbenzoate.

In U.S. patent N 4826829 and 4788207 describes some substituted ethinicity and their use as light-sensitive acaricides and insecticides. It is reported that when R including 2-(Tien-2-ylethynyl)benzothiophene (also called 2-(2-titilating)tianeptine). It is reported that launched bioassay of these compounds, but the results are not presented (Rossi et al. //Tetrahedron, 1984, 40, 2773).

An increasing number of scientific evidence that toxic reactions initiated by light, play an important role in the control of some pest populations. Over the past few years has been the development of the idea of using light-sensitive substances as insecticides and acaricides. Such photosensitizers are active due to the catalytic effect on the conversion of the basic triplet States of oxygen in the excited singlet state. The oxygen in the excited singlet state behaves as a highly active oxidizing agent that destroys the tissues of the insect, with which it is in contact, and, therefore, killing the insect or mite. As a consequence, the application of some light-sensitive compounds ethynylbenzoate is effective when used in the hearth, which is combating insects and mites. The high level of the activated light insecticidal and acaricidal activity of some of these compounds ethynylbenzoate has not previously been reported.

Join us ethynylbenzoate < / BR>
R1selected from hydrogen, halogen, lower alkyl, lower haloalkyl and phenylethylene group,

R2selected from hydrogen, halogen, lower allylthiourea, lower haloalkaline group, guidancearticle, lower alkoxycarbonyl, (lower alkoxycarbonyl-lower alkenyl)group, phenyl, 2-tanila and methyltin-2-Il,

R3selected from alkyl, lower trialkylsilyl, lower haloalkyl, oxyalkyl, alkylcarboxylic, methyltin-2-yl, 2-tanila and bestien-2-Il,

R4selected from hydrogen, halogen, lower alkyl, lower haloalkyl, low alkoxygroup, low haloalkylthio, lower alkoxycarbonyl, amino and lower alkylcarboxylic.

In the present description encountered the terms "halogen" and "halogen" means fluorine, chlorine, bromine and iodine. The definition of "low" before the term "alkyl", "alkoxygroup", etc. means that the alkyl is a straight or branched hydrocarbon chain with 1-6 carbon atoms. The term "halogen" before the term "alkyl", "alkoxygroup", etc. means that one or more hydrogen atoms replaced by halogen.

Among the compounds of ethynylbenzoate, which currently covers the I. Preferred compounds of the present invention are compounds in which R4represents chlorine, methyl, isopropyl, trifluoromethyl or hydrogen.

Active compounds of the present invention can be obtained by conventional methods known in the art. For example, these issues are addressed in: Takahashi et al. //Synthesis 1980, 627; Rossi et al. //Tetrahedron, 1984, 40, 2773; Cadogau. Organo Phosphorus Reagents in Organic Synthesis. New York: Academic Press, 1979, N 4, p. 155.

Example 1. Synthesis of 2-(Tien-2-ylethynyl)benzothiophene

Stage A. 2-Identifer

In nitrogen atmosphere mixed solution of 25.0 g (0,186 mol) of benzothiophene in 250 ml of dry tetrahydrofuran is cooled to -65oWith, and added dropwise over 69.8 ml (0,186 mol) n-utility (2.7 M in hexane), maintaining the temperature of the reaction mixture below -60oC. after the addition was finished the reaction mixture was stirred for 5 minutes and then allow to warm to 0oC. then added dropwise a solution 50,8 g (0,200 mol) of iodine in 180 ml of tetrahydrofuran, maintaining the temperature of the reaction mixture below 10oC. after the addition was finished the reaction mixture was allowed to warm to ambient temperature and stop the reaction with saturated aqueous solution of metabisulfite is washed with one portion of an aqueous saturated solution of sodium metabisulfite and one portion of aqueous saturated solution of sodium chloride. The aqueous layers were combined and washed with diethyl ether. The ether wash water is combined with the organic layer, and the combined product is dried with sodium sulfate. The mixture is filtered, and the filtrate concentrated at reduced pressure to a residue. The residue is dissolved in diethyl ether and again concentrated under reduced pressure to a residue. The residue is dissolved in warm hexane, and elute through a column of silica gel. The eluate concentrated under reduced pressure to a volume of approximately 100 ml, and the solution vykristallizovyvalas solid. The mixture is put, and collect the solid by filtration, and in two reception get out of 18.9 g of 2-identify.

Stage b 2-Trimethylsilylethynyl

In nitrogen atmosphere is stirred solution prepared by mixing 12.0 g (0,074 mol) of 2-bromothiophene, 9,9 g (0,092 mol) of trimethylsilylacetamide and 120 ml of triethylamine, and added 0.32 g of bis(triphenylphosphine)palladium (II) chloride (catalyst) and 0.28 g of copper iodide (I) (catalyst). After the addition was finished the reaction mixture was stirred at ambient temperature for 18 hours. Then the reaction mixture was concentrated under reduced pressure to a residue. The residue is dissolved is th water and one portion of saturated aqueous solution of sodium chloride. The organic layer is dried with sodium sulfate and filtered. The filtrate is concentrated at reduced pressure to a residue. The residue is subjected to a processing on a chromatographic column with silica gel. Elution performed using a 10% solution of methylene chloride in hexane. The appropriate fractions are combined and concentrated at reduced pressure, obtaining 11 g of 2-trimethylsilylmethylamine. The NMR spectrum was consistent with proposed structure.

Stage C. 2-Idenitifed

In nitrogen atmosphere is stirred solution of 3.3 g (0.018 mol) of 2-trimethylsilylmethylamine in 50 ml of tetrahydrofuran, and added 5.8 g (0.018 mol) of three-hydrate of tetrabutylammonium. Upon completion of addition the reaction mixture is stirred for 30 minutes. After that, the reaction mixture is move in 100 ml of water and extracted with three portions, each 75 ml diethyl ether. The combined extracts are washed with three portions of water and one portion of aqueous saturated solution of sodium chloride. The organic layer is filtered through silica gel, and the filtrate is dried with sodium sulfate. The mixture is filtered, and the filtrate is concentrated, resulting in total of 2.0 g of 2-idenitify. Stage a-b repeat a few times.

Stage, 2-(B, using of 4.2 g (to 0.016 mol) of 2-identify (obtained in the same manner as in example 1, stage A), 2.2 g (at 0.020 mol) of 2-idenitify (obtained in the same manner as in example 1, stage b) and a catalytic amount of bis(triphenylphosphine)palladium (II) chloride and copper iodide (I) in 50 ml of triethylamine. The yield of 2-(Tien-2-ylethynyl)benzothiophene is 3.5 grams, so pl. 114-116oC. the NMR spectrum was consistent with proposed structure.

Example 2. 2 2-[5-(4-Cryptomaterial)Tien-2-ylethynyl]benzothiophen

Stage A. 2-Trimethylsilylcyanation

This connection get the same way of example 1, step B, using of 40.9 g (of) 0.157 mol) of 2-identify (obtained in the same manner Kai in example 1, stage A), 17.0 g (0,173 mol) of trimethylsilylacetamide and catalytic amounts of bis(triphenylphosphine)palladium (II) chloride and copper iodide (I) in 400 ml of triethylamine. The resulting 2-trimethylsilylcyanation use in the following reaction, bypassing the stage of the selection.

Stage B. 2-(tion-2-ylethynyl)benzothiophene

The reaction mixture obtained in stage A, containing 2-trimethylsilylcyanation, mix, and add 4,96 g (0,0157 mol) of three-hydrate of tetrabutylammonium and 10.1 g (0.1 is food for 4.5 hours. Then, using a syringe, add 36,3 g (0,173 mol) of 2-idioten. Upon completion of addition the reaction mixture was stirred at ambient temperature for 60 hours. Then the reaction mixture was dissolved in diethyl ether and a small amount of methylene chloride and the solution washed with two portions of aqueous 10% ammonium chloride solution and one portion of water and one portion of aqueous saturated solution of sodium chloride. The organic layer is dried with sodium sulfate and filtered. The filtrate is concentrated at reduced pressure to a residue. The residue is subjected to a processing on a chromatographic column with silica gel. Elution performed with hexane and a mixture of 20% methylene chloride and hexane. The appropriate fractions are combined and concentrated at reduced pressure, obtaining in the end of 35.1 g of 2-(Tien-2-ylethynyl)benzothiophene.

Stage C. 2-(5-Jomtien-2-ylethynyl)benzothiophene

This connection get the same way of example 1, step A, using 10.0 g (0,0416 mol) of 2-(Tien-2-ylethynyl) benzothiophene, 20 ml (0,050 mol) n-utility (in the form of a 2.5 M solution in hexane) and 13.0 g (0,0549 mol) of iodine in 100 ml of tetrahydrofuran. The yield of 2-(5-Jomtien-2-ylethynyl)benzothiophene 9.5,

V. the teaching of example 1, stage B, using of 17.7 g (0,0787 mol) of 4-cryptomaterial, 10,9 g (0,111 mol) of trimethylsilylacetamide, and 0.62 g (0,0009 mol) of bis(triphenylphosphine)palladium (II) chloride and 0.34 g (0,00018 mol/iodide copper (I) in triethylamine. Output 1-(4-triptoreline)-2-trimethylsilylethynyl are 19.8, the NMR spectrum corresponds to the expected structure.

Stage D. 4-Triftormetilfullerenov

This connection get the same way of example 1, step B, using 19,0 g (0,0784 mol) of 1-(4-triptoreline)-2-trimethylsilylethynyl and 24.7 g (0,0784 mol) of three-hydrate of tetrabutylammonium in 200 ml of diethyl ether. The reaction mixture is filtered through silica gel and the silica gel washed with diethyl ether. The washing water and combine the filtrate, concentrated under reduced pressure and get 22.9 grams of essential concentrate, which constitute the bulk of 4-triftormetilfullerenov.

Stage E. 2-[4-Cryptomaterial)Tien-2-ylethynyl]benzothiophen

This connection get the same way of example 1, step B, using 0.5 g (0,0014 mol) of 2-(5-Jomtien-2-ylethynyl)benzothiophene (obtained in the same manner as in example 2, stage b), 0.26 g (0,0015 mol) 4-triftormetilfullerenov (obtained in this W is Yes copper (I) in triethylamine. The yield of 2-[5-(4-cryptomaterial)Tien-2-ylethynyl] benzothiophene 0.25 g, so pl. 149-150oC. the NMR spectrum was consistent with proposed structure.

Example 3. 2-(5-Methyltin-2-ylethynyl)benzothiophene

This connection get the same way of example 1, step A, using 0,050 g (0,0021 mol) of 2-(Tien-2-ylethynyl)benzothiophene (obtained in the same manner as in example 2, stage a and B), 0.33 g (0,0023 mol) methyl iodide and 1.5 ml (0,0023 mol) n-utillity in 10 ml of tetrahydrofuran. The yield of 2-(5-methyltin-2-ylethynyl)benzothiophene is 0.4 g; so pl. 85-87oC. the NMR spectrum was consistent with proposed structure.

Example 4. 2-(5-Penalties-2-ylethynyl)benzothiophene

Stage A. Tributyl-[5-(bestien-2-ylethynyl)Tien-2-yl]tin

This connection get the same way of example 1, step A, using 3.0 g (0,013 mol) of 2-(Tien-2-ylethynyl)benzothiophene (obtained in the same manner as in example 2, stage a and B), 4.7 g (0.014 mol) of the chloride of anti-and 5.5 ml (0.014 mol) of n-utility (2.5 M in hexane) in 30 ml of tetrahydrofuran. Output tributyl [5-(bestien-2-ylethynyl)Tien-2-yl]tin is 1.2,

Stage B. 2-(5-penalties-2-ylethynyl)benzothiophene

To a stirred solution of the Ana add a catalytic amount of bis(triphenylphosphine)palladium chloride (II). Upon completion of addition the reaction mixture is heated under reflux and with stirring for 18 hours. After that the reaction mixture is cooled to ambient temperature and then treated on a chromatographic column with silica gel. Elution is carried out with hexane. The appropriate fractions are combined and concentrated at reduced pressure, obtaining in the end, 0.28 g of 2(5-penalties-2-retail)benzothiophene; so pl. 185-186,5oC. the NMR spectrum was consistent with proposed structure.

Example 5. 2-(5-Formities-2-ylethynyl)benzothiophene

The mixed solution of 10 g (0,042 mol) of 2-(Tien-2-ylethynyl)benzothiophene (obtained in the same manner as in example 2, stage a and B) in 100 ml of tetrahydrofuran is cooled to -70oWith, and add portions of 20 ml (0,050 mol) n-utility (2.5 M in hexane), maintaining the temperature of the reaction mixture below -60oC. Upon completion of addition the reaction mixture is stirred for 45 minutes, while the temperature of the reaction mixture returned to the level of -70oC. then added 3.8 g (0,052 mol) of dimethylformamide. Upon completion of addition the reaction mixture was stirred at -70oC for 5 minutes and then allow to warm up on mania and washed successively with water and then saturated aqueous sodium chloride. The organic layer is then absorbed 15 g of silica gel, which is placed in the column of silica gel, and the length of the layer is 2.5 see perform Elution with a mixture of hexane and ethyl acetate in the ratio of 1:1. The eluate concentrated under reduced pressure to a solid residue brown. The dried solid residue is suspended in hexane, and the hexane decanted from the solids. The solid is dried, resulting in a total of 2.1 g of 2-(5-formities-2-ylethynyl)benzothiophene. The NMR spectrum was consistent with proposed structure.

Example 6. 2-[5-(4-Chlorpheniramine)Tien-2-ylethynyl]benzothiophen

Stage A. Diethyl(4-Chlorophenyl)hydroxymethylphosphonate

Under nitrogen atmosphere a solution of 20.0 g (0,143 mol) of 4-chlorobenzaldehyde and 19.7 g (0,142 mol) of diethylphosphate stirred at ambient temperature for 4 days. Analysis of the reaction mixture by gas chromatography shows that the reaction has not gone completely. Add 10 ml of triethylamine, and the reaction mixture is additionally stirred at ambient temperature for 4 days. Analysis of the reaction mixture by gas chromatography shows that the reaction mixture still not reacted completely. The reaction mixture is heated to 40-50othe best in the end of 39.2 g of diethyl-(4-chlorophenyl)hydroxymethylphosphonate.

Stage B. Diethyl-(4-chlorophenyl)chloromethylphosphonate

The mixed solution of 38.0 g (0,136 mol) of diethyl-(4-chlorophenyl)hydroxymethylphosphonate in 250 ml of methylene chloride cooled to 0oWith, and using a syringe add a solution of 18.8 g (0,158 mol) of thionyl chloride in 12 ml of methylene chloride. Upon completion of addition the reaction mixture was allowed to warm to ambient temperature and stirred for 60 hours. After that, the reaction mixture is washed with two portions diluted with water to 1 N. hydrochloric acid. The organic layer is filtered through silica gel. Silica gel elute with hexane:ethyl acetate (1:1). The combined filtrates are concentrated under reduced pressure, resulting in total of 40.5 g of diethyl-(4-chlorophenyl)chloromethylphosphonate. The NMR spectrum was consistent with proposed structure.

Stage C. 2-[5-(4-Chlorpheniramine)Tien-2-ylethynyl]benzothiophen

The mixed solution of 0.75 g (0,0028 mol) of 2-(5-formities-2-ylethynyl)benzothiophene and 0,83 g (0,0028 mol) of diethyl-(4-chlorophenyl)chloromethylphosphonate in 10 ml of dimethylformamide is cooled to 0oC, and add 0,94 g (0,0084 mol) of potassium tert-butylate. Upon completion of addition the reaction mixture was stirred at 0oC for 30 minutes, then allow to warm to the development on a chromatographic column with silica gel. Elution performed using hexane. The appropriate fractions are combined and concentrated at reduced pressure, obtaining in the end, 0.20 g of 2-[5-(4-chlorpheniramine)Tien-2-ylethynyl]benzothiophene; so pl. 189-191oC. the NMR spectrum was consistent with proposed structure.

Example 7. 2-[2-(4-Triptoreline)thiazole-5-ylethynyl]benzothiophen

Stage A. 4-Triptoreline

Mix a solution to 70.9 g (0,414 mol) of 4-triftormetilfosfinov and 60 ml (0.43 mol) of triethylamine in 400 ml of pyridine, and bubbled in him, hydrogen sulfide, while the course of the reaction is controlled by thin layer chromatography. When the analysis of the reaction mixture by thin layer chromatography shows that the reaction was completed, the addition of hydrogen sulfide ceased. Complete the addition of hydrogen sulfide requires approximately 7 hours. Upon completion of addition the reaction mixture was incubated for 60 hours, after which it is poured into a mixture of ice water. The resulting solid is collected by filtration and dissolved in diethyl ether. The solution was washed in turn with one portion of water, two 150 ml portions of aqueous 10% hydrochloric acid solution and one portion of water nasishennostyu concentrated under reduced pressure, receiving a result of 76.9 g of 4-triftormetilfosfinov. The NMR spectrum was consistent with proposed structure.

Stage B. 2-(4-Triptoreline)thiazole

The mixed solution of 5.0 g (0,024 mol) 4-triftormetilfosfinov, 4.4 g (0,026 mol) of bromoacetaldehyde and 4 drops of concentrated hydrochloric acid in 50 ml of ethanol is heated under reflux for 18 hours. After that, the reaction mixture is processed on a chromatographic column with silica gel. Elution performed using 20% solution of ethyl acetate in hexane. The appropriate fractions are combined and concentrated at reduced pressure, obtaining in the end of 3.3 g of 2-(4-triptoreline)thiazole. The NMR spectrum was consistent with proposed structure. The reaction is repeated several times.

Stage Century. 5-Iodine-2-(4-triptoreline)thiazole

This connection get the same way of example 1, step A, using 4.8 g (0,021 mol) of 2-(4-triptoreline)thiazole, and 12.2 ml (0,026 mol) n-utility (2.1 M in hexane) and 7.3 g (0,029 mol) of iodine in 98 ml of tetrahydrofuran. Output 5-iodine-2-(4-triptoreline)thiazole is 5.3, the NMR spectrum was consistent with proposed structure.

Stage, 2-[2-(4-Triptoreline) stadia B, using 1.5 g (0.04 mol) of 5-iodine-2-(4-triptoreline)thiazole, 0,86 g (0,005 mol) of 2-ethynylbenzoate (obtained in the same manner as in example 2, stage b) and a catalytic amount of bio(triphenylphosphine)palladium (II) chloride and copper iodide (I) in 15 ml of triethylamine. The yield of 2-[2-4(triptoreline)thiazole-5-ylethynyl] benzothiophene is 1.4 g; so pl. 178-180oC. the NMR spectrum was consistent with the proposed structure.

The following connections will be received, using similar techniques (see tab. 1-5).

Having insecticidal and acaricidal properties ethynylbenzene compounds of the present invention are typically not used in a free form without mixing or dilution with other substances, and are typically used in suitably composed of a composition compatible with the method of application and comprising effective for the manifestation of insecticidal or acaricidal properties number of connections ethynylbenzoate. Connection ethynylbenzoate of the present invention, like most pesticidal substances can be mixed with acceptable agricultural surface - active agents and carriers normally employed for facilitating disperse the activity of the material. Connection ethynylbenzoate of the present invention can be applied, for example, in the form of drugs for the shower, Farrukh Dustov or granules to the area in which it is required to conduct pest control, and the form in which they are used varies, of course, depending on the insect species and the environment. Thus, the compounds of ethynylbenzoate of the present invention may be introduced into the composition of forms, such as granules of large, powdered drugs, wettable powders, concentrates, capable of emulsification, solutions, etc.

The granules may contain porous or nonporous particles, such as, for example, attapulgite clay or sand, which serve as carriers for compounds ethynylbenzoate. The granules are relatively large, typically with a diameter of 400-2500 mm. Particles or impregnated with a compound ethynylbenzoate from a solution, or covered by the connection of ethynylbenzoate, and sometimes used the adhesive. Granules generally contain 0.05-10%, preferably 0.5 to 5% active ingredient an effective amount for the manifestation of insecticidal properties.

Dusty are mixtures of compounds ethynylbenzoate is it chalk, infusoria earth, calcium phosphates, carbonates of calcium and magnesium, sulfur, flours, and other organic or inorganic solids which act as carriers for insecticides and acaricides. These fine solids have an average particle size less than 50 microns. A typical dust formulation used for controlling insects contains 1 part of the compound and 99 parts of talc.

Connection ethynylbenzoate of the present invention can be manufactured in the form of liquid concentrates by dissolution or emulsification in suitable liquids and into solid concentrates by mixing with talc, clays, and other known solid carriers used in the technology of pesticides. The concentrates are compositions containing 5-50% connection ethynylbenzoate as an effective amount for the manifestation of insecticidal properties and 95-50% inert material, which includes surface-active dispersing, emulsifying and wetting agents, but for the purposes of the experiment can be used even higher concentrations of active ingredient. For practical application in the form of preparations for the shower concentree.

A typical recipe of 50% wettable powder containing 50% (weight) of the active ingredient, 22.0% of the diluent-attapulgite, 22.0% of the diluent-kaolin and 6% emulsifier sodium form of lignosulfonate produced during sulfate cooking pulp.

Typical carriers for solid concentrates (also known as wettable powders include fallerovo earth, clay, silica and other lightmachine inorganic diluents with high absorption properties. Formulation of solid concentrate suitable for combating insects and mites, contains as wetting agents, sodium lignosulfonate and sodium lauryl sulfate, 1.5 parts of each, 25 parts of active ingredient and 72 parts attapulgite clay.

Produced concentrates containing products of the present invention having a low melting point, suitable for transportation. Such concentrates receive by melting low-melting solid products together with one percent or more of the solvent to obtain a concentrate which does not harden when cooled to the freezing temperature of the pure product or to lower.

Suitable liquid concentrates represent the positions, easily dispersible in water or other liquid media. They may consist entirely of compounds benzothiophene and liquid or solid emulsifying agent, or they may also contain a liquid carrier such as xylene, heavy aromatic petroleum fractions, isophorone and other relatively non-volatile organic solvents. When applied, these concentrates are dispersed in water or other liquid carriers, and are typically used in the form of preparations for spraying on the spaces that are being processed.

A typical formulation concentrate (50 g per liter), capable of emulsification, will contain 5,90% (weight) of the active ingredient; as emulsifiers: 1,80% of a mixture of calcium salt codefilebaseclass and nonionic condensation product of polyoxyethylene (6-molar) with Nonylphenol, 2,70% mixture of the calcium salt of dodecylbenzenesulfonate nonionic condensation product of polyoxyethylene (30-molar) with Nonylphenol, 1,50% nonionic paste simple ether polyalkyleneglycol and 88,10% of the solvent is purified xylene.

Typical surface-active wetting, dispersing and emulsifying agents used in the formulation of pesticides include, reprimed; simple alkylaromatic alcohols; sulfates of higher alcohols; polyvinyl alcohols; polyethylene oxides; sulfonated animal and vegetable oils; sulfonated petroleum distillates; esters of fatty acids and polyhydric alcohols and addition products of ethylene oxide to such esters and addition products of ethylene oxide to long-chain mercaptans. Trading offers many other types of suitable surface-active substances. When using a surface-active substance is usually found in insecticidal or acaricidal composition in the amount of 1-15 wt.

Other suitable formulations are simple solutions of the active ingredient in a solvent in which this ingredient is completely dissolved to the desired concentration, such as acetone, or other organic solvents.

An effective amount of a compound of ethynylbenzoate for the manifestation of insecticidal or acaricidal properties, insecticidal or acaricidal composition diluted for application is normally from about 0.001 to wt. to about 8 wt. Many variants are known in the technology of compositions for spraying and gustovich compositions can be used in atively composition.

Insecticidal or acaricidal composition of the present invention can be formulated with other active ingredients, including other insecticides, nematicides, acaricides, fungicides, plant growth regulators, fertilizers, etc. using the composition for combating insects or acaridae you only need to focus where you want to be applied an effective amount of a compound of ethynylbenzoate for the manifestation of insecticidal or acaricidal properties of the compositions. Such lesions can be, for example, the insects, the plants on which the insects feed, or habitat for insects. When this focus is soil, for example, the soil in which crops grow or will be planted, the active compound may be in contact with the soil, and not necessarily be entered in it. In most applications, an effective amount or manifestations of insecticidal or acaricidal properties will be from about 50 to 750 g / ha, preferably from 150 g to 500 g per hectare.

Alkenylbenzene of the present invention were tested for insecticidal and acaricidal activity under ultraviolet light in the development of the cows /Epilachna vovivestis/, scoops no /Tvichoplusia ni/, scoops /Heliothis virescens (Fabvicius)/, and susceptible to the phosphates of klasika spider bimaculated /Tetranychus urtical/. Listed in the results of the testing activity is presented under the indexes BAW, SAW, MBB, CL, TBW and TSM-S, respectively. Insects and acarid stand in ultraviolet light (wavelength 320-400 nm, 1600-2400 w/cm2within 24 or 48 hours, using test procedures adapted for the entertainment of organisms participating in trials. Regardless of the test procedure, the hollow leaves of plants or leaves, removed from all plants are sprayed to runoff with an aqueous solution containing 10% acetone, 0.25% octylphenoxypolyethoxyethanol and 500 parts/thousand of the test compounds. For each applicable interest test is carried out twice.

Leaves infected adults of klasika spider bimaculated, remove from cultivated plants and cut into segments, each of which is 50-75 females Clasica. Each segment is placed on the upper surface of the leaf whole plant speckled beans (Phaseolus vulgaris). After the mites will move to a lower surface of leaves, remove the leaf segments, used for infection, and each of the races the nod to infection lexicom. After the plants will dry up, together with a pot placed under the hood on metal pallets and irradiated with ultraviolet light under the conditions described above. The supply of water to the pan supports turgescent plants. At the end of the exposure time, count the number of mites using a binocular microscope at approximately 10xincreased. Each sheet separated from the plants and placed on the table of the microscope. Count only living adult females on the reverse side of the sheet. Dying mites is considered dead. Note changes in the state of experimental plants, such as any loss from eating or toxic to plants exposure compared to control untreated plant.

In trials involving ladybugs, beet source of worms" South "of the original worms and scoop plants spotted beans are sprayed investigated chemikalien and leave to dry as previously described. Each pilot plants cut off at soil level, and the stem is pulled through the hole of small diameter, punched in the bottom of the wax container 226 grams (eight ounces). In each container count to ten larvae of the second stage of development, the containers to zakryvayuschimesya in the water during the exposure time. During exposure of plants subjected to the action of UV light, as described above. After lighting the containers open, and count the number of dead and live insects. Moribund larvae, which move randomly or can't crawl, they are considered as lost. Notes the state of the plant, such as any loss from eating or toxic to plants exposure compared to control untreated plant.

In table. 6 presents the results obtained in 48 hours. the lighting and the use of the proportion of active substance 50 part./thousand

1. Ethynylbenzoate formula I

< / BR>
where R is chosen from the group of formulas

< / BR>
R1hydrogen, halogen, lower alkyl, lower haloalkyl and phenylethynyl;

R2halogen, lower allylthiourea, lower haloalkyl, guidancearticle, lower alkoxycarbonyl, lower alkoxy-carbonyl-lower altergroup, phenyl, methylthieno-2-yl and 2-thienyl;

R3lower alkyl, lower tralkoxydim, lower haloalkyl, oxyalkyl, alkylsulphonyl, 2-thienyl, methylthieno-2-yl and bestien-2-yl;

R4hydrogen, halogen, lower alkyl, lower haloalkyl lowest alkoxygroup, lower holodeck is 1, wherein R is selected from 4-phenylethyl, hydrogen, lower haloalkyl.

3. Connection on p. 1, wherein R is selected from halogen, methylthiourea, phenyl and methylthieno-2-yl.

4. Connection on p. 1, wherein R is and R3selected from lower alkyl, 2-tanila and methyltin-2-yl.

5. Connection on p. 1, wherein R is and R4selected from hydrogen, chlorine, lower alkyl and trifloromethyl.

6. Connection on p. 1, wherein R1is 4-trifluoromethyl, R2phenyl, R3- 2-thienyl, R4trifluoromethyl.

 

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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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