Derivatives of 1-ellimination, the retrieval method, insecticidenematicides composition and method of combating insects, mites and nematodes

 

(57) Abstract:

Usage: agriculture, chemical plant protection products. The essence of the invention: Derivatives of ellimination I (radicals have the appropriate values). The method of obtaining the I-interaction reagent II alkylation, with the release of the product, or by processing the obtained salt of an appropriate reagent.

(1)

(2)

Insecticidenematicides composition comprises in wt.% the active - compound of formula (1) is 0.1 to 50, targeted supplements - the rest. In the method of combating insects, mites and nematodes used as a compound of formula (1) in an effective amount, in particular 0.1 to 21 kg/ha table 6.

The invention relates to new derivatives of 1-ellimination, to the way they are received, to insecticidenematicides compositions and to a method of combating agricultural pests, particularly ticks, with the soil or damaging the foliage insects, and nematodes.

Numerous substituted imidazole compounds which exhibit different forms of pesticide activity, including herbicide, fungicide, nematicidal, insecticidal and antibacterial, and also serve as regulators the tins according to European patent application N A, unsubstituted in the positions 2 and 4 of the imidazole ring, but with an additional phenyl substituent in position 5; 2-arylamidase with insecticide and other pesticide properties described in European patent application N A, in which the aryl ring is associated with the imidazole ring through the carbon atom in position 2 and not through the nitrogen atom, whereas the nitrogen in the first position substituted with hydrogen or, if necessary, the alkyl group. In U.S. patent N 4282238 also described imidazole derivatives exhibiting pesticidal activity.

However, all of these various pesticides have undesirable high phytotoxicity index, which leads researchers to develop new compounds with pesticidal activity with low toxicity, providing a high degree of safety when working with them and not hazardous to the environment and human health.

This goal is achieved by the new derivatives of 1-arielmeadow having the General formula 1:

< / BR>
in which X is S(0)nR1where R1represents a C1-C4alkyl, unsubstituted or partly or completely replaced by halogen atoms, and n = 0,1,2, Y odor is alkyl, R2-halogen, R3and R5hydrogen, R6-halogen, R4halogen, CF3, OCF3provided that if Y is hydrogen or Br,

Z is hydrogen or CH3< / BR>
R2and R6Is Cl or Br

R1CH3, CF3, CF2Cl or CFCl2,

n=0,1 or 2

R4differs from F3if Y is hydrogen, CL, Br, SCH3Z=H or CH3< / BR>
R2and R6=Cl, R1=CH3CH(CH3)2, CF3, CCl3, CF2Cl or FCl2,

n=0,1 or 2

R4differs from Cl, if Y=H, Z=H or CH3R2and R6=Cl, R1=CF3, CF2Cl or CFCl2n=0,1 or 2, R4differs from Cl if Y=H, Z=H or CH3R2and R6= Cl; R1=CF3, CF2Cl or CFCl2a n=0,1 or 2, R4differs from Br.

Of particular interest among the compounds of formula (1) are compounds that contain some specific substituents, has a positive effect in the sense of security for the environment and human health. Among these preferred compounds of formula (1), we can mention, for example, compounds in which Y=H, F, Cl, Br, J, N=CHOC2H5, SCH3, Z=H, CH3or2H5.

R
B4= F, or R4=Cl, Br, I, CF3or OCF3when Y=N=CHOC2H5, SCH3that a n=0, 1, or 2.

The invention relates also to a method for producing derivatives of 1-arielmeadow General formula 1 consists in the fact that the compound of formula 1B:

< / BR>
where X, Z, R2R6have the above significance, with X, Z and the amino group optionally protected, is subjected to diaminononane, for example, by treatment with alkylnitrates obtaining the appropriate diazonium salt and subsequent treatment of the obtained salt of the appropriate reagent to obtain the compounds of formula 1 where Y=hydrogen, halogen or alkylsulphonyl.

Compounds according to the invention have a high toxicity to arthropods, for example, ticks subclass Acari, especially Tetranychus urticae (bimaculated spider Clasica) or Panonychus ulmi (European spider Clasica).

Compounds of General formula (1) can be obtained using existing methods or their adaptation (i.e., the methods used in practice or described in the chemical literature): usually applied to formation of the imidazole ring and, if necessary, carry out the replacement of deputies. The term "protection" refers to igodit to loss of reactivity. When describing processes, the term "amino" means unsubstituted aminogroup (unless specified otherwise).

Cyclization begins with the appropriately substituted N-phenylimino compounds that cyclists under the influence of the reagent of the main character to N-phenylimidazoline intermediate products. This process, including subsequent initial conversion of the substituents Z and Y, can in General be represented in the form of the reaction of compounds of formula (III) with the agent of the main character, the result of which is formed a compound of the formula (IV):

< / BR>
where in the formula III:

R2, R3, R4, R5and R6have the same values as in formula 1,

X is hydrogen or haloalkyl, especially trifloromethyl,

Z is hydrogen, halogen, alkyl, haloalkyl or oxygraph, if necessary, in the isomeric ketoform, and

Q is cyano or lower alkoxycarbonyl, and in formula IV:

R2, R3, R4, R5and R6have the same values as in formula 1,

X is hydrogen or haloalkyl, especially trifloromethyl,

Y amino group, oxygraph (if necessary in the isomeric ketoform, if X is hydrogen or alkoxy - or haloalkoxy group obtained by alkylation of exigrep meniu can be obtained from compounds of formula (IV), as described below, by introducing appropriate substituents, in particular X,Z and y

Especially valuable intermediate compound of formula (I), (Ia):

< / BR>
in which X, R2, R3, R4, R5and R6have the values specified above can be obtained as follows (scheme I):

< / BR>
According to this scheme, the original product is usually a commercial alkyl-orthoformate (I) in which R'=C1-C4alkyl group, or a commercial aniline (2). As a catalyst upon receipt of formamidine (3) typically use an inorganic acid such as hydrochloric or organic acid, for example paratoluenesulfonyl. The reaction is carried out at a temperature of -20 to 180opreferably at 0-120oin the presence of an inert organic solvent, for example, any hydrocarbon, chlorinated hydrocarbon, aromatic hydrocarbon, ether, alcohol, etc., as well as alkalineforming. Formamide (3) may be present in the form of a mixture of regioisomers.

Intermediate product formamidine (4) are obtained by reaction of formamidine (3) aminoacetonitrile or its hydrochloric acid salt in the presence of a base inert organic solvent to obtain Gimli are alkoxides, hydroxides, hydrides, carbonates of alkaline or alkaline earth metals and amines such as Diisopropylamine, Tripropylamine etc. as solvents it is possible to use inert organic solvents, such as alcohols (e.g. methanol or ethanol), ethers (for example, diethylether, tetrahydrofuran, dioxane or diglyme), amine (for example, triethylamine or pyridine) or water, or a mixture of these solvents. The reaction is usually carried out at a temperature from -20 up to 180opreferably at about 20-120o.

Intermediate product formamidine (4) can be selected or collisional in situ to imidazole (5) without pre-allocating, by further processing the grounds under the above conditions. It is desirable to use for this purpose is sodium methoxide in methanol at 20-25o.

The reaction between imidazole (5) and sulfanilyl a halide, preferably chloride (R1S Gal, in which R1alkyl or haloalkyl), to obtain compound (6) it takes place in an inert abrotanum organic solvent, such as chlorinated hydrocarbons, ether, etc., preferably in dichloromethane, in the presence of acid acceptors, as pyridine, any tertiary amine of eimaste from the boiling point of sulphonylchloride and solvent.

Compounds according to the invention of General formula (1), in which X - alkylsulfanyl, haloalkaliphilic, alkylsulfonyl, haloalkylthio, alkylsulfonyl and haloalkaliphilic, Y is hydrogen, halogen, alkylsulfonyl, Z is hydrogen or alkyl, and R2, R3, R4, R5and R6have the meanings given above, can be obtained from compound (6): (see diagram 1).

Deamination of imidazole (6) carry out as a result of its reaction with an organic nitrite such as tert-butylnitrite, in an organic solvent (e.g. tetrahydrofuran) at a temperature of -20 to 180o, preferably between 10 and 100o.

The oxidation of sulfide (7), n=0, to the sulfoxide with n=1 or sulfone (8) with n=2 can be performed using an appropriate number of peracetic acid, cryptographically acid, m-chloroperbenzoic acid, hydrogen peroxide, a mixture of peracetic acid and hydrogen peroxide or peroxymonosulfate potassium, which is marketed under the name Oxon.. Usually the reaction is carried out in an inert organic solvent at a temperature from about -30 to 180o.

In addition to the above, the compound of formula (6) can be converted into other compounds coz the via with dominiruyushim agent, as described above, after which the compound (7) immediately enter into a reaction with an agent selected from bromoform, copper chloride or dimethyl disulfide with the formation of compounds of General formula (1) in which Y is a halogen atom or alkylsulfonyl group (n=0), a Z a hydrogen atom. The reaction is usually carried out in an inert organic solvent such as anhydrous acetonitrile, typically at a temperature of about -20 -180opreferably from 10 to 100o.

In an alternative method, compound (6) is transferred to the diazonium compound by the reaction of 5-amino derivatives with nitrous acid at a temperature below 5o. The subsequent collapse of the page in the presence of, for example, copper chloride, bromide, cyanide, or nitrite in the reaction of Sandmeyer leads to the formation of compounds of General formula (1) in which Y may be a chlorine atom or bromine, and Z is a hydrogen atom or alkyl. The compound of formula (1) in which Y alkoxyalkane group, get in the reaction of compounds of formula 1;

where Y is the amino group, with alkalineforming in the presence of acidic organic or inorganic catalyst at a temperature of from 0 to 120oor, if necessary, in an inert'or the weft and new connections.

Each compound was investigated using one or more methods of spectroscopic analysis (IR, NMR, GC/MS, etc) with the aim of characteristics and confirm their chemical structure.

Example A. Obtain 1-(2,6-dichloro-4-trifloromethyl)-5-amino-4-triftormetilfullerenov - idazole.

a) Obtaining ethyl-N-(2,6-dichloro-4-trifloromethyl)formamidine.

To 1,09 g (4.6 mmole) of 2,6-dichloro-4-trichoroethylene add concentrated Hcl (0,46 mmole) and 1.04 g (7.0 mmole) of triethylorthoformate. The resulting mixture is stirred, then heated to 85oand evaporated in vacuum. The residue is analyzed by NMR:1H NMR (CDCl3): of 1.42 (t, J=7.0 Hz, 3H), 4,47 (K, J=7,0 Hz, 2H), EUR 7.57 (s, 3H). This connection is used in the next stage without further purification.

b) Receiving cyanomethyl-N-(2,6-dichloro-4-trifloromethyl)formamidine.

In the solution of 20,20 g (0,218 mole) of aminoacetonitrile-hydrochloride in 500 ml of methanol add to 11.79 g (0,218 mole) of sodium methoxide at 0o. The mixture is stirred at room temperature for 30 min, then evaporated to dryness under vacuum. The residue is extracted twice with 400 ml of diethylether and the resulting ether solution is added to 62,45 g (0,218 mole) of EB is 400 ml of tetrahydrofuran and heated the mixture at the reflux temperature for 18 hours. After that, the solvent evaporated and the residue is separated into water and metaalgorithm phase. The organic layer is dried over anhydrous sodium sulfate to remove the solvent. The residue is purified by column flash chromatography with 20% ethyl acetate in hexane and elute 30% ethyl acetate in hexane to obtain 24 g of the desired product (yield 37,25%).

1H-NMR (DCl3): d and 4.40 (s, 2H), 7,55 (s, 2H), to 7.59 (s, 1H).

C) Obtaining 1-(2,6-dichloro-4-trifloromethyl)-5-aminoimidazole.

To a solution of 4.4 g (14,91 mmole) cyanomethyl-N-(2,6-dichloro-4-trifloromethyl)formamidine in 400 ml of methanol added 81 g (14,91 mmole) of sodium methoxide at 4o. The mixture is stirred for 3 hours at the temperature of distillation. Then it evaporated to a dry residue with the formation of the final product with a yield of 100%

1H NMR (DCl3/acetone-d6): d of 3.43 (s, 2H), of 6.68 (s, 1H), 7,28 (s, 1H), 7,88 (2N).

g) Obtaining 1-(2,6-dichloro-4-trifloromethyl)-5-amino-4-Tripropylamine - dazole.

To a solution of 4.8 g (14,91 mole) of 1-(2,6-dichloro-4-trifloromethyl)-5-aminoimidazole in 400 ml of methylene chloride add 1.3 ml (14,91 mole) trifloromethyl-chloride at 0o. Then estimates the water and divide the mixture into water and methylenchloride phase. The organic layer is dried over anhydrous sodium sulfate to remove the solvent. The residue is subjected to recrystallization from methylene chloride with the formation 3,36 g of the desired product with a melting point of 134o(exit 52,51%).

Elementary analysis: C11H5Cl2F6N3S

Calculated: 33,35; N 1.27MM; N 10,61; S 8,09;

Found: 33,54, N 1,20, N 10,67, S Of 8.37.

Example E. Obtain 1-(2,6-dichloro-4-trifloromethyl)-5-amino-2-chloro-4-trifloromethyl - phenylimidazole.

To a solution of 6.0 g (br15.15 mole) of 1-(2,6-dichloro-4-trifloromethyl)-5-amino-4-Tripropylamine - dazole in 100 ml of methylene chloride add to 1.70 ml (18,18 mmole) Sulfuryl-chloride at 0o. The resulting mixture within 5 days stirred at room temperature under nitrogen atmosphere. After that, the mixture is treated with water, and then divided into methylenchloride and the aqueous fraction with sodium bicarbonate solution. The organic layer is dried over anhydrous sodium sulfate to remove the solvent. The residue is purified by column chromatography using 20% ethyl acetate in hexane, obtaining 1.9 g of the desired product with a melting point 172,5owith the release of 31,62%

Example Century. Obtain 1-(2,6-dichloro-4-triptoreline)-5-amino-2-chloro-4-trifloromethyl - phenylimidazole in 40 ml of tetrahydrofuran added 2.76 ml (23,2 mmole) of tributylamine. The resulting mixture is heated at room temperature in nitrogen atmosphere for 2 hours. The mixture is then evaporated to a dry residue, which is purified by column chromatography using 10% solution of ethyl acetate in hexane. Produced 1.6 g of the desired product with a melting point 112owith the release of 83,0%

Elementary analysis: C11H3Cl3F6N3S

Calculated: 31,71, N OF 0.68, N 6,75, F 27,65;

Example, Obtaining 1-(2,6-dichloro-4-trifluromethyl)-2-chloro-4-Tripropylamine - dazole.

To a solution of 800 mg (1,93 mmole) 1-(2,6-dichloro-4-trifloromethyl)- -2-chloro-4-trifluromethanesulfonate in triperoxonane the acid is added to 0.20 ml of 30% hydrogen peroxide at 0o. The resulting mixture was stirred at 0ofor 4 hours and then at room temperature for 50 hours. The mixture is then evaporated at room temperature and the residue is distributed between methylene chloride and saturated aqueous solution of sodium bisulfite. The organic layer was washed with aqueous sodium bicarbonate solution and evaporated the remaining organic phase. The residue is purified using column flash chromatography on silica gel in 5% ethyl acetate in hexane. After the 47,5owhen the output 36,02%

Elementary analysis: C11H3Cl3F6N2OS

Calculated: 30,61; H 0,70; N Of 6.49; Cl 24,64; F 26,41; S 7,43.

Found: 30.63 Per; N 0,83; N 6,48; CL 24,83; F 26,53; S 7,78.

Example D. Obtain 1-(2,6-dichloro-4-trifluromethyl)-2-chloro-4-trifluromethanesulfonate - dazole.

To a solution of 300 mg (0.72 mmole) of 1-(2,6-dichloro-3-triptoreline)-2-chloro-4-trifluromethanesulfonate - dazole in 5 ml triperoxonane acids are added 0.15 ml (1.44 mmole) of 30% hydrogen peroxide at 0o. The resulting mixture was stirred at room temperature for 4 days. Then it is evaporated to remove triperoxonane acid, and the residue is treated with methylene chloride and saturated aqueous sodium bicarbonate. The organic layer was washed with aqueous sodium bicarbonate solution. Then it is dried over anhydrous sodium sulfate to remove the solvent. The residue is purified by preparative thin-layer chromatography using 100% methylene chloride to education 190 mg of the desired product with a melting point 182,5oand output 59,03%

Example E. Obtain 1-(2,6-dichloro-4-triptoreline)-2-chloro-5-methylsulfanyl-4-triflora - methylsulfonylmethane.o. The mixture was stirred at 0ofor 15 minutes and then at room temperature for 45 minutes dilute its 75 ml of methylene chloride and distributed between methylene chloride and water. The organic layer is dried over anhydrous sodium sulfate to remove the solvent. The residue is purified preparative TLC in 5% ethyl acetate in hexane. Formed 480 mg of the desired product (yield 58,74%).1H NMR (CDCl3): d and 2.26 (s, 3H), 7,82 (s, 2H).

Example J. Obtain 1-(2,6-dichloro-4-trifloromethyl)-5-amino-2-bromo-4-trifloromethyl - phenylimidazole.

To a solution of 1.35 g (3,40 mmole) 1-(2,6-dichloro-4-triptoreline)-5-amino-4-Tripropylamine - dazole in 20 ml of chloroform, add 0.5 ml (9,76 mmole) of bromine. The mixture is stirred at room temperature and under nitrogen atmosphere for 2 hours, evaporated to remove excess bromine and treat the residue with water and methylene chloride. The organic layer is dried over anhydrous sodium sulfate, removing the solvent. The residue is purified using column flash chromatography on silica gel, 7% ethyl acetate in hexane, receiving 200 mg of the desired product with a melting point 154oand output 13,62%

Example 3. Obtain 1-(2,6-dichloro-4-trifloromethyl)-5-bromo-4-triformis alpenlite - dazole in 10 ml of acetonitrile was added 1 ml of bromoform and 1.20 ml (10,10 mol) tert-butylnitrite at 0o. The mixture is stirred at room temperature under nitrogen atmosphere for 1.5 hours. Add 10 ml of toluene and evaporated to dryness under vacuum. The residue is purified column chromatography on silica gel in 5% ethyl acetate in hexane. Formed 800 mg of the desired product with a melting point of 87.5 when entering 34,44%

Elementary analysis: C11B3BrCl2F6N2S

Calculated: OF 28.72; N 0,66; N 6,09; F 24,78; S 6,97;

Found: Depreciation Is 29.06; N 0,69; N 6,20; F 24,2; S Of 7.48.

Example I. Obtain 1-(6-chloro-2-methylsulfanyl-4-triptoreline)-2-bromo-4-glandiforme - Tinsulanonda.

To a solution of 500 mg (0,984 mmole) 1-(2,6-dichloro-4-triptoreline)-2-bromo-4-chloromethanesulfonyl - imidazole in 2 ml of tetrahydrofuran, add a solution of 69 mg (0,984 mmole) methanolate sodium in 0.3 ml of water. The resulting mixture was stirred at room temperature for 14 hours, then treated with titilation and water. The organic layer is separated and dried over anhydrous sodium sulfate to remove the solvent. The resulting residue is purified using preparative thin-layer chromatography in a solution of ethyl acetate in hexane (20%). Obtain 180 mg of the desired product having a melting point of 116owith:

a) Obtaining N-acetyl-2,6-dichloro-4-Tripropylamine.

To 10.6 g (of 0.26 mol) of dry potassium hydride in THF (150 ml) was added 20 g (87,3 mmole) of 2,6-dichloro-4-trichoroethylene at 0oin nitrogen atmosphere. The resulting mixture is stirred and heated for 3.5 hours at room temperature. The mixture is then cooled to 0oand added dropwise into it and 6.6 ml (92,8 mmole) acetylchloride. The mixture was stirred at 0ofor 30 minutes and Then again heated at room temperature in a nitrogen atmosphere over night. The mixture is treated with saturated solution of NH4Cl (150 ml) and evaporated to remove THF, and the remaining suspension is filtered and washed from the solids with hexane, then washed with dichloromethane, getting 14.5 g of the final product with a yield of 61%

1H NMR (CDCl3/CD3OD:) d a 2.12 (s, 3H), 7,60 (s, 2H).

b) Obtain 1-chloro-1-methyl-N-(2,6-dichloro-4-trifloromethyl)formimino.

To a suspension of 4.3 g (15.8 mmole) of N-acetyl-2,6-dichloro-4-Tripropylamine in 50 ml of chloroform added to 3.3 g (15.8 mmole) petaluridae phosphorus at room temperature. After that, the mixture is heated to reflux under nitrogen atmosphere for 1 hour. The mixture is then evaporated to a dry residue. To poslednata. Then it is evaporated to obtain a dry residue, which is purified by column chromatography on silica gel in a solution of ethyl acetate in hexane (10%). The result is 4.3 g of the desired product in the form of oil. Output 93.7% of Range1H NMR (DCl3): d 2,70 (s, 3H), 7,58 (s, 2H).

C) Obtaining 1-(2,6-dichloro-4-trifloromethyl)-5-amino-2-methylimidazole.

To a solution of 9.6 g (33,0 mmole) of 1-chloro-1-methyl-N-(2,6-dichloro-4-trifloromethyl)formimino in 300 ml of chloroform added 3.7 g (66,0 mmole) of aminoacetonitrile at room temperature. The resulting mixture is heated to reflux temperature under nitrogen atmosphere for 60 hours. Then the reaction mixture was used without additional purification in the following procedure. According to NMR spectrometry using1H during the described process converts about 60% of the original imidocloprid.1H NMR (CDCl3): d to 2.13 (s, 3H), return of 6.58 (s, 1H), 7,76 (s, 2H).

g) Obtaining 1-(2,6-dichloro-4-triptoreline)-5-amino-2-methyl-4-chlorodifluoromethyl - sulfanilimide.

In the reaction mixture obtained in the previous stage add 5.8 ml (57,7 mmole) Chlorodifluoromethane-chloride at room temperature. Then the mixture at the same temperature paramesh the Organic layer is dried over anhydrous sodium sulfate, mpariwa solvent prior to the formation of the final product. The latter, without additional purification, used in the next reaction stage.

d) 1-(2,6-dichloro-4-triptoreline)-2-methyl-4-Chlorodifluoromethane - imidazole.

The crude product obtained in the previous phase, is mixed with 100 ml of THF, and then add 19,6 ml (165 mmole) of tert - butylnitrite. The mixture was stirred at the reflux temperature in a nitrogen atmosphere, leaving at night in the dark place. After that, the mixture is evaporated to a dry residue. The latter is cleaned by column flash chromatography using a 10% solution of ethyl acetate in hexane. The result of 1.3 g of the desired product having a melting point 118,5o. Output per imidocloprid described in stage b) of 9.4%

Using similar methods, were obtained the following compounds 1-68, whose characteristics are shown in table 1. It shows a group of compounds, the joint nature of the substitution on the phenolic ring. Thus, according to the substitution in the phenol ring, table 2 shows the following groups:

Presents the melting point of the individual compounds are average values, wikilanguage compounds according to the invention as miticides, insecticides and nematicides.

Using the compounds of examples 1-68, spent testirovanie their pesticidal activity and studied the possibility of applying for the control of mites, nematodes and some insects, including aphids, caterpillars, house flies and larvae of three species of beetles (two feeding on the foliage, and one, damaging the roots). Below in the table. 3 lists the species for which testing took place.

The types of songs

Compounds according to examples 1-69 tested in the form of ready-made forms, which, depending on the used test procedures, was prepared as follows:

For the control of mites, aphids, marching worm and Mexican leaf was applied a solution or suspension, which was obtained by adding 10 mg of the test compound in the solution containing 160 mg of dimethylformamide, 838 mg of acetone, 2 mg of a mixture of Triton X-172 and Triton X-152 in the ratio of 3:1 (anionic and nonionic emulsifiers, characterized weak foaming properties, each of which is a mixture of alkilammonievymi alcohols with organic sulfonates) and 98,99 g of water. The final concentration of the test compound in suspension or solution was 100 parts per m is balali in a mixture of only 16.3 g of water, accordingly reducing the content of other components. The final concentration of test compounds was 200 parts per million. To obtain preparations containing 100 parts of test compound per million, this mixture was diluted with an equal volume of 20% (by weight) solution of sucrose in water. If necessary, the finished form was treated with ultrasound to ensure complete dispersion of the components.

When tested on the larvae of the beetle flea beetle, a solution or suspension was prepared as described in the previous paragraph for house flies. The original drug containing 200 parts of test compound per million, then diluted with water to obtain the concentration required in a particular test.

When testing for tuberous nematode, as well as during system testing on the Colorado potato beetle, marching scoop and the cotton is ready, the source solution was prepared by adding 15 mg of the test compound to 250 mg of dimethylformamide, 1250 mg of acetone and 3 mg of the above mixture of emulsifiers. Then add water to a final volume of 45 ml, which provided the concentration of the test compound 333 parts per million. If necessary, complete dispersion of mixture components was achieved ULV, evaluated their pesticidal activity depending on the concentration (parts per million by weight), using the following methods.

Bimaculated the spider Klasik:

Affected adults or nymphs bimaculated spider Clasica from the mother culture sheets were placed on the primary leaves of two plants beans, vynashivalsya in peat pots (6 cm). For 24 hours on fresh plants transferred to 150-200 ticks that was enough for testing. Varasimavichene in pots plants (one for each test compound) were placed on a rotating table and was treated with 100 ml of the drug contained the test compound at a concentration of 100 parts per million. The plant is watered so that it flowed excess fluid. For this purpose used the sprayer of DeVilbiss at a pressure of about 276 kPa. The control processing affected lexicom plants produced with 100 ml aqueous mixture of acetone, dimethylformamide and emulsifiers that do not contain the test compound. The other served as control treatment commercial technical preparation of dicofol or hexythiazox in the same mixture. Treated plants were left for 6 days, the child ovicidal activity):

Eggs were obtained from adult bimaculated spider Clasica from the mother culture. Strongly affected by mites leaves were placed on fresh bean plant. After oviposition, females eggs for 24 hours, the leaves were immersed in a solution of tetraethyl diphosphate to destroy mobile forms and prevent further egg laying. This procedure, which was repeated after drying, the leaves did not affect the viability of the eggs. Plants in pots were placed on a rotating table (one for each test compound) and was treated with 100 ml of a preparation containing the test compound at a concentration of 100 parts per million. The plant is watered so that it flowed excess fluid. For this purpose used the sprayer of DeVilbiss at air pressure of about 276 kPa. The control processing carried out with 100 ml of a mixture of water, acetone, dimethylformamide and emulsifiers, not containing the test compounds. As the standard used processing commercial technical preparation of demeton in the same mixture. Treated plants were left for 7 days, and then counted the number of nonviable eggs, also taking into account the residual activity of Testino kruchininoj aphids were reared on plants dwarf nasturtiums in pots. Plants (one for each test compound) were infected 100-150 aphids were then placed on a rotating table and sprayed with 100 ml of a mixture containing 100 parts of test compound per million, by using a sprayer of DeVilbiss at air pressure of about 276 kPa. As control was used a mixture of water, acetone, dimethylformamide and emulsifiers, not containing the test compounds. Standard served as the commercial preparation of technical Malathion in the same mixture. After treatment, the pots with plants were left for one day, and then counted the number of dead aphids.

Marching scoop:

varasimavichene potted bean plants were placed on a rotating table and was treated with 100 ml containing 100 parts of test compound per million, using a sprayer Devilish at air pressure of about 276 kPa. The control processing carried out with a mixture of water, acetone, dimethylformamide and emulsifiers, which did not contain the test compounds. Standard served as the commercial preparation of technical cypermethrin or sulprofos, in the same ready form, and that the tested compounds. The dry leaves were placed in plastic cups, lined inside uvlag second stage, the Cup was closed and left for 5 days. The larvae are unable to move the length of his own body, even with the boost, presumed dead.

Marching scoop and Colorado potato beetle on tomatoes (assessment system activity):

This test was performed in conjunction with the assessment of the activity of compounds against root nematodes (see below). Plant tomatoes, varasimavichene in the soil for evaluating the effect of test compounds on nematodes (when the initial concentration of the soil in terms of screening of 13.2 parts per million or approximately 150 parts per million in the used solution), and then used to study the penetration of these compounds in the leaves of tomato through the root system with the participation of the transport mechanisms of the system. After testing with the nematode leaves were cut, placed in a plastic container and were infected with the larvae of the second stage marching scoops. After 5 days, the estimated mortality of larvae in percent. The sheets on which was massive loss of Cutworm larvae were fed with larvae of the Colorado potato beetle the second stage. 2 days later evaluated the mortality of grubs in percent.

Checkpoint bollworm and cotton aphids on cotton and sorghum (assessment system activity):

About the Les which if necessary, diluted to provide a concentration in soil of 10 parts per million with the introduction of 5 ml of the product to moisturize pots (6 cm), which was cultivated sorghum or cotton. Of cotton plants infected cotton aphids for 2 days before testing. About 4 days after trials evaluated the mortality of these insects. The leaves of cotton and sorghum were cut, placed in plastic containers and infected larvae marching scoops the second stage. Mortality of larvae in percentage was evaluated after approximately 5 days after the start of the test.

Mexican leaf:

Varasimavichene potted bean plants were placed on a rotating table and apilevel 100 ml containing 100 parts of test compound per million, so that excess fluid dripping from the plants. Used for this purpose sprayer Devilish when the air pressure of the order of 276 kPa. Control spraying is carried out with a mixture of water, acetone, dimethylformamide and emulsifiers, not containing the test compounds. Standard served as commercial preparations of technical cypermethrin or sulprofos in the same mixture. The dry leaves were placed in plastic cups lined isnad Mexican leaf, then the Cup was closed and left for 5 days. Upon expiry of this period was estimated maggots, which were considered dead if they could not travel the length of his own body, even with the boost.

House fly:

Adult house flies at the age of 4-6 days received as indicated in the Specifications of the Association of chemical producers (Blue Book. McNair-Dorland. N. Y. 1954, 243-244) under conditions of controlled breeding. Flies immobilizerpower by anesthesia with carbon dioxide. 25 mobilisierung individuals of both sexes were placed in mesh Sadok, covered with wrapping paper. 10 ml, containing 100 parts of test compound per million, was placed in a Cup with absorbent cotton swab. In the control experiment used a mixture of water, acetone, dimethylformamide and emulsifiers, not containing the test compounds. The treatment produced a similar way. Standard served as a commercial technical preparation of Malathion in the same mixture. The Cup with the bait placed in the fish tank before replanting it shot insects. After 24 hours was assessed by the test result, counting the dead flies, which were not recovered the ability to move the held sample with the test compound (nominal concentration of 200 parts per million), which were bred in such a way as to provide the desired concentration in the soil. The breeding produced with 3.2 ml of water. At the same time in the vessel was placed 5 germinating corn kernels. The contents of the vessel are thoroughly mixed by shaking to ensure a uniform distribution of all components of the test system. Then in the deeper soil was placed 20 eggs of the beetle flea beetle.

This deepening was placed 1 ml of vermiculite and 1.7 ml of water. Similarly shaped test system, which was treated with a mixture of water, acetone, dimethylformamide and emulsifiers, not containing the test compounds. Standard served as one of the commercial technical preparations, for example, terbufos, fonofos, Fort, chlorpyrifos, carbofuran, isazofos or isoprop, in the same form as the test compound. After 7 days produced a count of the surviving larvae, using a well-known method of extraction in the funnel "Berles".

Tuber nematode:

The roots of tomato plants infected with the eggs of tuberous nematodes were collected from the mother culture and purified from the soil, first by shaking, and then rinsing with tap water. Eggs of nematodes were separated from the root cloth which was filled with liquid so to its upper surface in contact with the sieve. Juveniles of the vessel was collected on a fine-meshed sieve. The hole at the bottom of the conical tank corked large-grained vermiculite and filled it with pasteurized soil in an amount of about 200 ml, so that the upper layer of 1.5 cm is below the top edge of the tank. In a hole made in the soil in the center of a conical vessel with a pipette and poured drug test compounds at a concentration of 333 parts per million. As the standard used commercial technical preparation of fenamiphos prepared in the same manner as the preparation of the tested compounds. As control was used the same test system, which was treated with a mixture of water, acetone, dimethylformamide and emulsifiers, which did not contain the test compounds. Immediately after treatment with a solution of the test compounds on the soil surface in each cone-shaped vessel was placed in 1000 larvae of the second stage of root nematodes. After 3 days in each vessel was transferred to one fresh tomato seedling. A vessel with such a seedling in the soil, infected larvae of the nematodes, for 3 weeks were placed in the greenhouse. At the end polyzoa scale, based on the comparison of the number of the Gauls with the observed in the control experiments.

Discerned:

1) intensive Gallo education comparable with that observed in the control test system;

3) weak Gallo education

4) very weak Gallo education

5) lack of Gallo-education, i.e. the absolute effectiveness of the drug.

On the basis of the obtained results was calculated indices U3or U5(effective dose, decrease the intensity of the Gallo-education to 3 or 5 points on the above scale).

Usually, as well as in field trials, cooked 50% concentrated suspensions of the test compounds, containing 500 g of active ingredient per litre. The composition of these preparations are given in table. 4.

The following discusses the results of the tests miticidal, insecticidal and nematicidal activities of some of the most significant compounds in accordance with examples 1-68. In table.2 shows examples of individual compounds that were instrumental in the fight against tested species of mites, nematodes and insects, these doses. In the table used abbreviations decoded above, the Sign "X" is the Number of compounds according to the invention has the additional miticidal properties bimaculated spider Clasica. In particular, the compounds according to examples 2, 3, 4, 5, 7, 11, 13, 14, 30, 36, 37 and 43 at a concentration of 100 parts per million have residual toxicity (50-100%) for hatched larvae in the test ovicidal activity on the grip. In addition, the proposed connection can be used to combat other types of mites. In particular, the compound from example 4 in field trials in the form of the preparation described above in the description of standard test procedures, in concentrations of 10-20 g active ingredient/l caused the death of 60 to 95% of individuals of European red Clasica (Panonychus ulmi) when spraying separately growing Apple trees.

Some of the compounds are characterized by a systemic effect on aphids and larvae of other insects after introduction into the root system at concentrations in the soil mentioned in the above in the test protocols. Obtained, in particular, the following results when using the compounds according to examples 19 and 33 celebrated the death of 30-100% of larvae marching scoops and/or the Colorado potato beetle on tomato plants; the use of compounds according to example 33 the death of 30-69% of larvae marching scoops on the sorghum plants, and the use of the compounds according to example 19 the death of 30%-69% cotton aphids on relocatefile ED3when they checked on tuber nematode are 13-21 kg/ha.

Compounds according to the invention can be used to combat a variety of pests even at lower doses than indicated above. For example, the rate of flow during the processing of the leaves may be reduced from 50-0,5 ppm and even below, when used in the composition of the lure to 50-0,05 ppm and less, and soil to 1.0-0.01 parts per million and less.

In the above tests and the results included in table.2, the compounds according to the invention was used in different concentrations. Processing of foliage solutions, suspensions or emulsions at a concentration of active compound of 1 part per million parts of the finished product is roughly equivalent to the soil at the rate of 1 g/ha (in terms of the content of the active ingredient with the intensity of 1000 l spray/ha, which is sufficient for application to plants such number of preparations in which the excess drains from the leaves). Thus, treatment of the foliage by spraying solutions or suspensions containing the active compound in concentrations from 6.25 to 500 parts per million, there is unity in its upper layer depth 7.5cm one part per million, the consumption rate of the medication should be 1000 g/ha

Methods of application and composition of drugs.

As follows from the above examples the use of the compounds according to the invention as pesticides, it relates to compounds having pesticidal activity, and methods of use thereof to combat a variety of pests, including arthropods, especially insects and mites, plant nematode, helminth and protozoa. Thus, the proposed connection can be used in practice, for example for protection against pests of agricultural plants, horticulture, forestry, veterinary medicine, animal husbandry and public health.

The invention relates to methods of pest control in the lesions, which consist in processing (in particular through the application or introduction) of effective amounts of compounds with the General formula (1), preferably formula (II), which contain the above-described substituents. The term "lesion" includes both the pests and their location, which inhabits feeds or one or the other species (plant, animal, human, field structure, housing, forest the organisations according to the present invention are intended primarily for controlling soil insects, in particular leaf beetles, termites (especially when the protection of buildings), the fly larvae, wireworms, beetles, weevils, sverlilnie, juices, root aphids, larvae of other insect species. They can also be used for combating plant pathogenic nematodes, including root, root-knot, onion, stem and other forms of these worms. When combating soil pests optimal methods of using these compounds are applied on the soil surface or are made in effective concentrations before sowing or planting or under the already growing culture. Connections can also be used for treatment of seeds or root system of the plants.

In addition, the compounds according to the invention is recommended for application to foliage or for use against arthropods, especially some species of insects and mites that feed on above-ground parts of plants, systemic impact. Another method of combating arthropods affecting the aboveground parts of the plant are the treatment of seeds or root system, after which pesticides are transported to the leaves and other organs.

Compounds according nastoem flies and other unwanted or harmful species of Diptera, such as house flies, horse flies, gadfly, different types of flies of gigalos and livinec, scatopsidae, midges, biting midges, mosquitoes, etc.

Protection of various kinds of products during storage, in particular of grain or flour, the various crops of groundnuts, feed for agricultural animals, as well as wood, household goods (such as carpets and fabrics). The proposed connection can be useful for mass outbreaks of and/or activity of certain groups of arthropods such as beetles, weevils, moths or mites. In particular, they can be recommended to combat or reduce the number Epheslia spp. (mill of liquidation), anthrenus (Anthrenus spp.), small meal hrusica (Jribolium spp.)

beetles that destroy grain stocks (Sotophilus), mites (Acarus spp.).

Compounds according to the invention can be used to combat roaches, ants and termites or other arthropods, residential and industrial premises, as well as mosquito larvae in streams, wells, reservoirs, and other water bodies with stagnant or running water. In agriculture, against adults, larvae and eggs of Lepidoptera (butterflies and moths), e.g. Heliothis spp. including Heliothis vir scoop), Mamestra configurata (marching scoop), Earias spp. OAD. E. insilana (boxed worm), Pectinophora spp. OAD. Pectinophora gossypiella (the box.the worm), Ostrinia spp. for example nubilalis (corn borer), Trichoplusia ni (scoop), Artogela spp. (kapust. scoop), Laphygma spp. (marching scoop), Agrotis and Amathes spp. (scoops), Wiseana spp. (the moth), Chilo spp. (Ognevka) Tryporyza spp. and Diatraea spp. (sugar and rice the liquidation) Sparganothis pilleriana (grape moth), Cydia pomonella (Codling moth), Archips spp. (fruit moth), Plutella xylostella (Diamondback moth), Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella. Plutella maculipennis. Malacosoma neustia. Euproctis hrysorrhoea, Lymantria spp. Bucculatrix thurberiella, Phyllocnistis citrella. Euxoa. spp. Feltia brassicae, Panolis flameea, Prodenia litura, Carpocapsa pomonella, Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Tineola bisselliella, Tinea pellionella, Hofmannophila pseudospretella, Cacoecia podana, Capus reticulana, Choristoneura fumiferana, Clysia ambiguellis, Homona magnanime and Tortix viridana.

Against adults and larvae of Coleoptera (beetles), e.g. Hypothenemus hampei (coffee grinder), Hylesinus spp. (beetles), Anthonomus spp. e.g., grandis (boxed worm), Acalymma spp. (beetle blaska), Lema spp. (Psylliodes spp. Leptinotarsa decemlineata (Colorado potato beetle), Diabrotica spp. (leaf), Gonocephalum spp. (false. the wireworm) Agtiotes spp. Limonius spp (wireworm) Dermolepida spp. Popillia spp. Heteronychus spp. (khruschak), Phaedon cochleariae (horseradish leaf), Epitrix spp. (beetle blaska), Lissorhoptrus oryzophilus (rice weevil), Meligethes spp. (pollen beetle) Ceutorhynchus spp. Rhynchophorus and Clachna varivestis. Atomaria spp. Oryzaephilus surinamensis, Sitophilus spp. Otiorrhynchus sulcatus. Cosmoplites sordidus. Ceuthorrhynchus assimilis. Hypera postica. Dermestes spp. Trogoderma spp. Anthrenus spp. Attgenus spp. Lyctus spp. Maligethes aeneus. Ptinus spp. Niptus hololeucrus. Gibbium psylloides, Tribolium spp. Tenebrio molitor, Conoderus spp. Melolontha melolontha. Amphimallon solstitialis and Costelytra zealandica.

Against Heteroptera (Hemiptera and Homoptera), nab. PsyIIa spp. Bemisia spp. Trialeurodes spp. Aphis spp. Myzus spp. Megoura viciae, Phylloxera spp. Adelges spp. Phorodon humuli (aphid cholevidae), Aeneolamia spp. Neptotettix spp. (rice Cicada), Empoasca spp. Nilaparvata spp. Perkinsiella spp. Pyrilla spp. Aonidiella spp. (San Jose scale). Coccus spp. Pseucoccus spp. Helopeltis spp. (bug), Lygus spp. Dysdercus spp. Oxycarenus spp. Nezara spp. Eurygaster spp. Piesma guadrata, Cimex lectulatius. Rhodnius prolixus and Triatoma spp. Aspidiotus hederae, Aerodes brasiicae, Brevicoryne brasiicae, Cryptomyzus ribis, Doralis fabae, Doralis pomi. Eriosoma lanigerum. Hyalopterus arundinis, Mactosiphum avenae. Phorodon humuli, Rhopalosiphum padi, Euscelis bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus.

Against Hymenoptera, nab. Athalia spp. and Cephus spp. (Sawfly) Atta spp. (ants). Diprion spp. Hopolocampa spp. Lasius spp. Monomorium spp. Polistes spp. Vespa spp. Hot spp. and Solenopsis spp.

Against Diptera. OAD. Delia spp. (larvae), Atherigona spp. and Chlorops spp. Sarcophaga spp. Musca spp. Phormia spp. Aedes spp. Anophele spp. Simulium spp. (jagalchi), Phytomyza spp. (miners), Ceratitis spp. (the fruit. fly) Culex spp. Drosophila melanogastes, Ceratitis capitata. Dacus oleae. Tipula paludosa, Calliphora erythrocephala, Lucilia spp. Chrysomyia spp. Cuterebra spp. Gastrophilus spp. Hyppobosca spp. Stomoxys spp. Oestrus spp. Hypoderma spp. Tabanus spp. Faniia spp. Bibio hortulanus. Oscinella frit, Phorbia spp. Pegomyia hyosceani.

and crickets), Gryllus spp. and Acheta spp. e.g. Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blatella germanica, Acheta domesticus, Gryllotalpa spp. Locusta migratoria migratoriordes. Melanoplus differentialis Schistocerca gregaria.

Against Collembola and Sminthurus spp. OAD. Onychiurus spp. (negaholic) Periplaneta spp. and Blatella spp. (cockroaches).

Against revnotrialc: Odontotermes spp. Reticuletermes spp. Coptotermes spp. (termites).

Against Dermaptera: Forticuls sp. (earwig).

Against arthropod pests of agricultural crops, including Acari (mites): Tetranychus spp. Panonychus spp. Bryobia spp. (spider mites), Ornithonyssus spp. (bird mites) Eriophyes spp. (haloorange ticks) Polyphadotarsonemus supp.

Against the Thysanura, for example Lepisma saccharia.

Against the Anoplura, for example Phylloxera vastatrix, Pemphigus spp. Pediculus humanus corporis. Haematopinus spp. and Linognathus spp.

Against the Mallophaga, for example, Trichodectes spp. and Damalinea spp.

Against Siphonoptera, for example Xenopsylla cheopis Ceratophyllus spp.

Against other arthropods, including Blaniulus spp. (millipedes) Scutigerella spp. (simfinity), Oniscus spp. (woodlice), Triops spp. (crustacea).

Against the Isopoda, for example, Oniseus asellus, Armadilidium vulgare and Porcellio scaber.

Against the Chilopoda, for example Geophilus carpophagus Scutigera spex.

As mentioned previously, the invention concerns methods of pest control by application or administration of effective amounts of compounds of formulas (1) on or in the pockets of the insects, mites or nematodes pests of plants the method of application may be reduced, for example, to the processing plants or the environment of their growth effective amounts of one or another connection. The range of effective concentrations of the proposed compounds ranges from 0.005 to 15 kg active ingredient/ha Optimal consumption rate is usually determined by a combination of factors, which belongs to the species of pest, type or stage of development of the affected plants, inter-row spacing, processing method, etc., the Preferred rate of application of the compounds according to the invention, when dealing with different groups of pests varies from 0.01 kg/ha to about 2 kg/ha.

When combating soil pests, the active compound, usually in the form of the finished product evenly distribute any suitable manner over the entire area to be processed (for example, when a solid or continuous processing), or only the areas immediately adjacent to the plants or embedded in the ground seeds. Distributed on the soil surface preparation goes into it or artificial, for this purpose, irrigation, or under the influence of natural precipitation. Processing can be performed both before sowing illprepared suitable for seed treatment before sowing. In this case, the action of drugs is manifested after sowing or in the process of plant growth. In addition, the composition can be applied to parts of plants, remote from the location of pests (for example, in the case of drugs for systemic effects, which treat the root system of plants or seeds before sowing killing insects, feeding on foliage).

In practice, the compounds according to the invention are usually used in the finished forms and preparations. The compositions contain at least one of the compounds according to the invention as an active ingredient in combination with one or more compatible components which role can perform, in particular, solid and liquid carriers or solvents, adjuvants, surfactants and other substances suitable for the purposes of this processing and which is acceptable from the point of view of agricultural use. Such compositions, are prepared by any known method, are also subject of the present invention.

The compositions may include other ingredients, such as protective colloid materials, adhesive agents, thickeners, thixotropic agents, substances, moviesarena to increase stability in the soil), sequestered agents and other substances. Generally speaking, the compounds according to the invention can be combined with any solid or liquid additives, which are used in the technologies of production of ready-made forms.

Compositions suitable for use in agriculture, horticulture and related industries, are manufactured in the form of preparations intended for spraying in liquid form, use the form Farrukh Dustov, granules, emulsions, preparations for fumigation etc.

Solid and liquid bait for combating arthropods contain one or more compounds of formula (1) and a carrier or solvent, which you can use food or other material which can be eaten active connection.

The effective dose of the active compounds using the proposed methods vary within very wide limits and depend primarily on the species of the pest or pathogen and severity of the lesion (e.g., crops). In General, the preparations according to the invention contain from 0.05% to 95% (by weight) of one or more active ingredients, from 1 to 95% of one or more solid or liquid carriers and, but-active substances, etc.

In this context, the term "carrier" denotes an organic or inorganic compound, natural or synthetic, in combination with which is the active ingredient that facilitates application of the latter, such as plants, seeds or soil. The media generally inert and should be suitable, depending on the purpose of the processing, agricultural or other use, in particular not to cause damage to plants.

As media use solid materials, such as clays, natural and synthetic silicates, silica, resins, waxes, solid fertilizers (in particular ammonium salt), ground natural minerals (kaolin, clay, talc, chalk, quartz, attapulgite, montmorillonite, diatomaceous earth, ground synthetic materials (silicon, or aluminum silicates, particularly silicates of aluminum and silicon). As solid carriers for granular preparations used crushed and crushed rock (including calcite, marble, pumice, thick and dolomite), synthetic granules of the nutrients of organic and inorganic origin, granules of such organic materials, like sawdust, shell coke nuts, sergeantat calcium, crushed tube or gas soot, water-soluble polymers, resins and wax, or, finally, solid fertilizers. If necessary, the composition of such solid compositions include one or more wetting or dispersing agents, emulsifiers, dyes and other materials that can simultaneously play the role of solid diluents.

The media can be liquid. In this case, using, for example, water, alcohols, especially butanol or glycol), their ethers and esters (especially methylglycol-acetate), ketones (especially acetone, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone or isophorone), individual fractions of oil (for example, paraffin or aromatic hydrocarbons, particularly xylenes or alkylnaphthalene), mineral and vegetable oils, aliphatic hydrocarbons (especially chlorobenzol), water-soluble or strongly polar solvents of the type of dimethylformamide, dimethyl sulfoxide or N-methylpyrrolidone, liquefied gases and other materials or mixtures of different composition.

Surfactants can be used as emulsifiers, dispersing or wetting agents. For this purpose apply, in particular, salts of polyacrylic sour is noxide with fatty alcohols or fatty acids, or fatty esters and fatty amines, substituted phenols (especially ALKYLPHENOLS and kilfenora), salts of esters sulfonterol acid derivative taurine (in particular alliterate), fotonya esters of alcohols or polycondensate of ethylene oxide with phenols and ethers of fatty acids with polyols, as well as functional sulphate, sulphonate or phosphate derivatives of these compounds. Especially important is the inclusion of ready-made forms at least one surface-active substance in cases where the active ingredient and/or the inert carrier are poorly soluble in water, not dissolve in it, while the finished product is intended for application with water.

In addition to the above components, the preparations according to the invention can contain other substances, in particular adhesive, and dyes.

Examples of liquid preparations are aqueous and non-aqueous solutions or suspensions (e.g., emulsifiable concentrates, emulsions, solutions, suspensions and fluid composition.

The content of the active ingredient in liquid preparations, for example in the form of soluble or emulsifiable concentrates usually ranges from 5 to 80% (by weight),P> Liquid preparations according to the invention in the form of suspensions and emulsions, as well as mixtures of spray applied (e.g., crops), mainly by spraying at the rate of 100-1200 l of fertilizer per hectare. Depending on the purpose of the processing and the techniques used, the rate can be increased or decreased (including the use of small and extremely small amounts of the drug).

Concentrated suspensions for spraying is prepared in such a way as to obtain a stable fluid product which does not asserted due to the high degree of dispersion and typically contains from 10 to 75 weight percent of active ingredient, from 0.5 to 30% surface-active agents, from 0.1 to 10% of thixotropic agents, from 0 to 30% of the necessary additives, such as antinoopolis agents, corrosion inhibitors, stabilizers, adhesion and increases the permeability of the substance and, as a carrier, water or an organic liquid in which the active ingredient is poorly soluble or insoluble. To prevent sedimentation or as antifreeze to water is sometimes added solid organic materials or inorganic salts, which are soluble in the carrier.

Smace is the active ingredient, from 20 to 90% solid carrier, from 0 to 5% of wetting agent, from 3 to 10% dispersing agent, and optionally, from 0 to 80% of one or more stabilizing and/or other additives, including substances that increase the permeability, dyes, adhesing and preventing the aggregation of connections, etc. To obtain such wettable powders, the active ingredients are thoroughly mixed in the mixer with additional material which may be impregnated on the fillers and ground in mills or other crushers, Thus obtained powders are characterized by high wettability and suspenderbelt. They can be suspended in water to obtain products with desired concentration of active ingredient, and the resulting suspension to use for high-quality processing of foliage.

"Dispersible in water granules" (DVG), i.e., granules, easily dispersible in water, have a composition very similar to that of the wettable powders. They are obtained by granulating ready-made forms in the form of wettable powders or dry (pressing after crushing and sieving) or wet (if you contact the thorough grinding the active ingredient with an inert filali binder, followed by drying and sieving).

Used when processing the dose of the active ingredient (effective dose) in the composition of the finished product is usually 0.005 to 15 kg/ha, preferably from 0.01 to 2 kg/ha As a rule, drugs to control arthropod, plant nematode, helminth and protozoa contain from 0.00001% to 95%, more frequently, from 0.0005 to 50 percent by weight of one or more compounds of General formula (1) or all of the active ingredients.

The following examples 70-77 illustrate part of the preparations for combating arthropods, especially mites and insects, as well as with plant nematode, helminth and protozoa, comprising as the active ingredient comprises the compounds with the General formula (1). All products presented in the examples 70-77, dissolve in water to form suitable for spray forms with concentration of active ingredients, which are necessary for carrying out treatments in the field. Below in the table. 5 given the General chemical characteristics of the ingredients in the formulations described in examples 70-77 (the content of individual components are given in weight percent).

Example 70.

Water-soluble concentrate has the following composition:

Active is dobavlaut active ingredient, heating and stirring the mixture until complete dissolution of the components. The resulting solution was brought to final volume of the organic.

Example 71.

Emulsifiable concentrate has the following composition:

The active ingredient 7%

Suprior BSU 4%

Arylan CA 4%

N-organic 50%

Solvesso 150 35%

The first three components dissolved in N-organic, after which add up to a final volume of Solvesso 150.

Example 72;

Wettable powder has the following composition:

The active ingredient 40%

Arilan 2%

Darvon N 2 5%

Celite PF 53%

These ingredients are mixed and milled in a hammer mill to obtain a powder with a particle size of not more than 50 microns.

Example 73.

Flowing water preparation has the following composition:

The active ingredient 40,0%

Atilan CPU 1,00%

Apropos 7360 0,20%

The glycol 5.00% per

Redigel 230 0,15%

Water 53,65%

These ingredients are thoroughly mixed and milled in a ball mill to obtain a particle size less than 3 microns.

Example 74.

Emulsifiable suspension (concentrate) has the following composition:

Active ingredientsyou and pulverized in a ball mill to obtain particles of an average size less than 3 microns.

Example 75.

Dispersible in water, the granules have the following composition:

The active ingredient 30%

Darvon N 2 15%

Arilan WITH 8%

Celite PF 47%

These ingredients are mixed and finely dispersed in water mill, after which the rotary pressing machine under the conditions of irrigation water (up to 10% ) produce granules. Last dried to remove excess moisture.

Example 76.

Dostum has the following composition:

The active ingredient 1-10%

Surmeli talc 90-99%

These ingredients are thoroughly mixed and subjected to further grinding to obtain a fine powder. The latter can be used for treatment of lesions arthropods, such as waste disposal sites or waste rock stored food products and household goods.

Processing of dust it is recommended to use mechanical ventilators, handheld vibrators or devices to Samoobrona cattle.

Example 77.

Wettable powder has the following composition:

The active ingredient 50%

Atilan CPU 5%

Aerosil 5%

Zeolite PF 40%

Atilan CPU absorb on Eurasiasemenova powder, which is then diluted with water to a concentration of 0.001-2 wt% of the active compound and is applied to the lesion arthropods, for example, larvae of Diptera, or plant nematodes, by spraying.

1. Derivatives of 1-arielmeadow formula I

< / BR>
where X is S (O)nR1where R1C1C4- alkyl, unsubstituted or partly or completely replaced by halogen atoms, n 0,1,2;

Y is hydrogen, halogen, C1WITH4alkylthio, ethoxy - C1WITH4-alkylidene;

Z is hydrogen, C1WITH4alkyl;

R2halogen;

R3and R5hydrogen;

R6halogen;

R4halogen, CF3, OCF3provided that if Y is hydrogen or Br, Z is hydrogen or CH3, R2and R6Cl or Br, R1CH3, CF3, CF2Cl or CFCl2n is 0,1 or 2, R4differs from OCF3if Y is hydrogen, Cl, Br, SCH3Z is H or CH3, R2and R6Cl, R1CH3CH(CH3)2, CF3, CCl3, CF2Cl or CFCl2n is 0,1 or 2, R4differs from Cl, if Y H, Z H or CH3, R2and R6Cl, R1CF3, CF2Cl or CFCl2n is 0,1 or 2, R4differs from Cl, if Y H, Z H or CH3, R/P>2. The compound of formula I on p. 1,

where Y is H, F, Cl, Br, I, CHOC N2H5, SCH3, Z H, CH3or C2H5. R1CF3, CCl2F CClF2, CHCl2, CHClF or CHF2, R2F, Cl, Br, R4F or R4Cl, Br, I, CF3or OCF3when Y CHOC N2H5, SCH3n is 0,1 or 2.

3. The method of obtaining derivatives of 1-arielmeadow General formula I on p. 1, characterized in that the compound of formula IB

< / BR>
where X, Z, R2R6have the specified values, with X, Z and the amino group optionally protected,

are diaminononane, for example, by treatment with alkyllithium obtaining the appropriate diazonium salt and subsequent treatment of the obtained salt of the appropriate reagent to obtain the compounds of formula I, where Y is hydrogen, halogen or alkylsulphonyl.

4. Insecticidenematicides composition comprising the active principle - derived 1-arylamidase and target additives, characterized in that as the derived 1-arylamidase it contains a compound of formula I under item 1 with the following ingredients, wt.

The active principle of 0.1 50

The target additive and the Rest

5. The composition according to p. 4 to combat chlenistonogi sulfanyl-4-chloromethanesulfonyl, 1-(2,4,6-trichlorophenyl)-5-methylsulfanyl-4 - dichloropropionanilide, 1-(2,6-sodium dichloro-4-forefeel)-5 - bromo-4-dichloropropionanilide, 1-(2,6-sodium dichloro-4 - forefeel)-5-methylsulfanyl-4-dichloropropionanilide, 1-(2,6-sodium dichloro-4-forefeel)-5-bromo-4-trifloromethyl sulfanilimide, 1-(2,6-sodium dichloro-4-forefeel)-5 - chloro-4-dichloropropionanilide, 1-(2,6-sodium dichloro-4 - forefeel)-5-bromo-4-chlorodimethylvinylsilane, 1-(2,4,6-trichlorophenyl) -5-ethoxymethyleneamino-4-dichloropropionanilide, 1-(2-bromo-4,6-dichlorophenyl)-5 - methylsulfanyl-4-dichloropropionanilide 1-(2-bromo-4,6-dichlorophenyl) -5-methylsulfanyl-4-trifluromethanesulfonate, 1-(2,6-dibromo-4 - forefeel)-5 - bromo-4-chlorodimethylvinylsilane, 1-(2,6-sodium dichloro-4 - forefeel)-5-bromo-4-dichloropropionanilide, 1-(2,6-sodium dichloro-4-forefeel)-5-bromo-4-trifluromethanesulfonate, 1-(2,6-sodium dichloro-4 - forefeel)-5 - bromo-4-dichlorophenol methylsulfonylamino, 1-(4-bromo-2,6 - dichlorophenyl)-5-methylsulfanyl-4-dichloropropionanilide or 1-(2,4,6-trichlorophenyl)-5-methylsulfanyl-4 - chloromethanesulfonyl.

6. A method of combating insects, mites and nematodes through the use of the compound of formula I through p. 1 in an effective amount.

7. The method according to p. 6, characterized in that the derivative of 1-elimidate used in an amount of 0.1 to 21 kg/ha

 

Same patents:

The invention relates to new 2-imidazolin-2-yl)thieno - foroperational compounds, to intermediates used to obtain these compounds, and the way of dealing with these compounds with unwanted annual and perennial plants, namely 6-(2-imidazolin-2-yl)thieno - and furo[2,3-b] and 5-(2-imidazolin-2-yl)thieno - and furo[3,2-b]the pyridine compounds and the corresponding 2,3-dihydrothieno and 2,3-dihydropyrimidine with structural formulas (Ia) and (Ib):

< / BR>
whererepresents a single or double bond; R1represents a C1-C4alkyl; R2represents a C1-C4alkyl or C3-C6cycloalkyl; R1and R2together with the carbon atom to which they are joined, can form WITH3-C6cycloalkyl, optionally substituted stands; And represents СООR3CHO, CH2OH, COCH2HE, CONHCH2CH2OH, CONHOH or

R3hydrogen, C1-C12alkyl, which can be broken od is alkoxy, halogen, hydroxyl, C3-C6cycloalkyl, benzyloxy, fullam, phenyl, furfuryl, galopera, lower alkylphenyl, lower alkoxyphenyl, nitrophenyl, carboxyla, lower alkoxycarbonyl, cyano, C1-C4alkylthio or three (lower) alkylammonium; C3-C6alkenyl, optionally substituted by one of the following groups:1-C3alkoxy, phenyl, halogen or two WITH1-C3alkoxygroup or two halogen groups; C3-C6cyclooctyl, optionally substituted by one or two1-C3alkyl groups; C3-C10quinil, optionally substituted by phenyl, halogen or CH2IT; or the cation of an alkali metal or alkaline-earth metal (CA, BA) manganese, copper, iron, ammonium, or organic ammonium; RWITHand RDrepresent N or CH3; Represents N; COR4or SO2R5provided that when a represents a COR4or SO2R5and is a СOOR3the radical R3cannot be hydrogen or a salt-forming cation; R4represents a C1-C11alkyl, chloromethyl or phenyl, optionally substituted A5 alkyl or phenyl, optionally substituted one metalno, chloro - or nitro-group; W represents 0 or S; X represents 0, S or whenis a single bond, the group S 0; Y and Y', Z and Z' represent hydrogen, halogen, C1-C6alkyl, C1-C4hydroxy (lower) alkyl, C1-C6alkoxy, C1-C6acyloxy, benzoyloxy, optionally substituted by one or two1-C4alkyl, C1-C4alkoxygroup or halogen; C1-C4alkylthio, phenoxy,1-C4haloalkyl,1-C4haloalkoxy, nitro, cyano, C1-C4alkylamino,1-C4dialkylamino,1-C4alkylsulfonyl or phenyl, optionally substituted by one or more1-C4the alkyl, C1-C4alkoxy, halogen, or any combination of these two groups, where Y and Z are the same provided that Y and Z represent hydrogen, halogen, alkyl or alkoxy, and when Y and Y' or Z and Z' are the same group they are hydrogen or alkyl; and taken together, Y and Z form a ring in which YZ has the structural formula -(CH2)n- where n являе/www.fips.ru/fullimg/rupat2/19962/004.dwl/2058313-8t.gif" ALIGN="ABSMIDDLE">-=where L, M, Q, and R7each represent hydrogen, halogen, nitro, C1-C4lower alkyl, C1-C4lower alkoxy, methoxy, phenyl, phenoxy, provided that only one of the radicals L, M, Q or R7may have a value different from hydrogen, halogen, C1-C4the alkyl or C1-C4alkoxy; or a pyridine-N-oxides, when W represents oxygen or sulfur and a is COOR3; and when R1and R2not the same, the optical isomers of these compounds, except for the case when R3represents a salt-forming cation, their salts kislotoustoichivam

The invention relates to herbicide compositions, in particular for a synergistic herbicide composition having a high herbicide effect on upland fields, and to a method of controlling weeds, especially broadleaf

The invention relates to a new derivative of imidazolidine, namely TRANS-4,5-guidemegreen-2-ONU formula (I) exhibiting fungicidal activity, and which may find application in agriculture

The invention relates to new derivatives of 1-phenylimidazole formula 1

CFN< / BR>
where R represents a hydrogen atom or methyl;

x represents a fluorine atom, a chlorine atom or a nitro-group;

y represents a fluorine atom or a chlorine atom;

z represents a hydrogen atom, a fluorine atom, a chlorine atom or a bromine atom, a process for the preparation of these compounds and insecticides containing as active components of these compounds

The invention relates to new derivatives of pyridinemethanol formula RNI where R1represents a hydrogen atom, a C1-C3-alkyl; R2is1-C4-haloalkyl; R3represents a halogen atom, trifluoromethyl; R4is1-C3-haloalkyl, the method of obtaining these compounds and insecticides containing these compounds as active ingredients

The invention relates to compounds of imidazole

The invention relates to organic chemistry, namely to a new connection, the hydrochloride of the enol 2 pinacolato-4(5)-methylimidazole-2 of the formula I

< / BR>
Compound I has astragalina activity and can be used to stimulate growth of wheat

FIELD: organic chemistry, herbicides, agriculture.

SUBSTANCE: invention relates to new substituted benzoylketones of the general formula (I): , all possible tautomeric forms and possible salts that can represent active substance as a component of herbicide agent. In the formula (I) A means (C1-C4)-alkyl; R1 means cyclo-(C3-C6)-alkyl; R2 means hydrogen atom (H), cyano-group (CN); R3 means hydrogen atom (H), halogen atom, CF3, (C1-C4)-alkylsulfonyl; R4 means halogen atom; X means groups: or wherein R5 means (C1-C4)-alkyl, (C1-C4)-alkoxy-group, (C1-C4)-alkylthio-group, di-(C1-C6-alkyl)-amino-group; R6 means (C1-C4)-alkyl, (C1-C4)-alkoxy-group, cyclo-(C3-C6)-alkyl; n = 0 or 1 including all possible tautomeric forms and possible salts. Compounds of the formula (I) elicit herbicide activity and can be used in herbicide composition.

EFFECT: valuable properties of compounds.

3 cl, 1 sch, 3 tbl, 13 ex

FIELD: organic chemistry, herbicides, agriculture.

SUBSTANCE: invention describes a synergistic composition of herbicides comprising components (A) and (B) wherein (A) represents herbicide taken among the group of the formula (I):

wherein R1 means (C1-C4)-alkyl; R2 means (C1-C4)-alkyl; R3 means hydrogen atom; X and Y mean (C1-C4)-alkoxy-group; (B) represents one or two herbicides taken among the group of compounds or their acceptable forms: alachlor, metolachlor, acetochlor, dimetenamide, atrazine, cyanasin, metribusin, fluthiamide, nicosulfuron, rimsulfuron, primisulfuron, pendimetalin, sulcotrion, dicamba, mesotrion, isoxachlortol, metosulam, anilofos, fenoxaprop-ethyl, setoxydim, diclofop-methyl, MCPA, bromoxynil, pyridat, clopyralid, iodosulfuron-methyl, ethoxysulfuron, amidosulfuron, gluphosinat-amminium, isopropylammonium-glyphosate, imasetapir wherein components (A) and (B) are taken in the effective doses. Also, invention describes a method for control of weeds by using above indicated herbicide composition. Invention provides the development of the synergistic herbicide composition eliciting high activity.

EFFECT: improved method for control, valuable properties of composition.

6 cl, 26 tbl, 3 ex

FIELD: organic chemistry, herbicides, agriculture.

SUBSTANCE: invention describes substituted benzoylcyclohexanediones of the general formula (I):

wherein m = 0 or 1; n = 0 or 1; A means a single bond or alkanediyl (alkylene) with 1-4 carbon atoms; R1 means hydrogen atom or unsubstituted alkyl with from 1 to 6 carbon atoms; R2 means methyl; R3 means hydrogen atom, nitro-, cyano-group, halogen atom, alkyl with from 1 to 4 carbon atoms substituted with halogen atom, alkoxy-group with from 1 to 4 carbon atoms or alkyl sulfonyl with from 1 to 4 carbon atoms; R4 means nitro-group, halogen atom, unsubstituted alkyl with from 1 to 4 carbon atoms of that substituted with halogen atom; Z means heterocycle, and herbicide agent based on thereof. Also, invention describes substituted derivatives of benzoic acid of the general formula (III):

wherein values n, A, R3, R4 and Z are given above. These compounds represent the parent substances used for preparing compound of the formula (I). Compounds of the formula (I) elicit high and selective herbicide activity.

EFFECT: valuable properties of compounds.

7 cl, 8 tbl, 7 ex

FIELD: organic chemistry, agriculture.

SUBSTANCE: invention relates to selective herbicidal compositions, containing customary auxiliary substances, as well as: a) herbicidal effective amount of compound of formula I or agriculture acceptable salt thereof wherein R are independently C1-C6-alkyl, C1-C6-haloalkyl, C1-C4-alcoxy-C1-C4-alkyl, or C1-C4-alcoxy-C1-C4-alcoxy-C1-C4-alkyl; m = 2; Q is group of formula wherein R23 is hydroxyl and Y is C1-C4-alkylen bridge; and b) synergetically effective amount of one or more herbicides; and methods for controlling of undesired plants in tame cultures using the said composition. Also disclosed is composition containing customary auxiliary substances, as well as herbicidal and synergetically effective amount of 4-hydroxy-3-(2-methyl-6-trifluoromethylpyridine-3-carbonyl)bicyclo[3.2.1]octo-3-ene-2-one of formula 2.2 and herbicidal antagonistically effective amount of antidote of formula 3.1. Compositions based on 4-hydroxy-3-(2-methyl-6-trifluoromethylpyridine-3-carbonyl)bicyclo[3.2.1]octo-3-ene-2-one and herbicidal antagonistically effective amount of antidote, as well as methods for controlling of weeds and cereal grasses in tame cultures also are described.

EFFECT: compositions useful in effective controlling of many weeds both in pre-spring and post-spring phases.

5 cl, 63 tbl, 12 ex

FIELD: agriculture, fungicides.

SUBSTANCE: claimed method includes treatment of contaminated cultural plants or cultivation area thereof with effective amount of composition, containing A) N-sulfonylvaline amide of formula I 1, wherein R1 represents hydrogen or haloprenyl; and R1 represents C1-C4-alkyl, in combination with B) methalaxyl, or fluozinam, or mancoceb, or chlorithalonyl, or strobyluzine, or pyraclostrobine, or acibenzolar-S-methyl, or dimethoform, or fludioxonyl, or cimoxanyl, or imazalyl in synergistically effective amounts. Fungicide composition containing effective combination of A and B in synergistically effective amounts in combination with agriculturally acceptable carrier and optionally with surfactant.

EFFECT: composition of increased fungicidal action due to synergic effect.

8 cl, 12 ex

Herbicidal agent // 2271659

FIELD: organic chemistry, agriculture, herbicides.

SUBSTANCE: invention relates to herbicidal agent containing compound of general formula I wherein X represents residue X1 or X2 and Z, R1 and R2 are as defined in claim of invention, and additional active substance selected from group containing bromoxynil, dicamba, flufenacete, metolachlor, atrazine, pendimethaline, imazetapir, iodosulfuron, nicosulfuron, 2-amino-4-(1-fluoro-1-methyl)-6-(3-phenyl-1-cyclobuthyl-1-propylamino)-1,3,5-triazine and N-[(4,6-dimethoxy-pyrimidine-2-yl)-aminocarbonyl]-2-dimethylamino-carbonyl-5-formyl-benzenesulfonamide. Compound of formula I and additional active substance are taken in mass ratio of 1:20-10:1, respectively.

EFFECT: agent of high herbicidal activity.

6 cl, 15 ex

FIELD: organic chemistry, chemical technology, medicine, veterinary science.

SUBSTANCE: invention describes the compound R-(-)-1-[2-(7-chlorobenzo[b]thiophene-3-ylmethoxy)-2-(2,4-dichlorophenyl)ethyl]-1H-imidazole of the formula (I) and its salts, in particular, its mononitrate. Also, invention relates to a method for preparing compound of the formula (I) possessing antifungal effect based on compound of the formula (I), and using compound of the formula (I) as an active component of the antifungal composition. Compound of the formula (I) can be used in compositions for treatment of fungal infections in humans or animals and against diseases of agricultural crops.

EFFECT: improved preparing method, valuable properties of compound and composition.

15 cl, 1 tbl, 10 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: agriculture.

SUBSTANCE: synergetic herbicide composition contains active substances such as chlorimuron-ethyl (I) and imazetapir (II) and salts thereof, used in the ratio of (I):(II)-10:1, and also contains fillers, diluents, surfactants and other functional additives needed for producing of preparation forms. Method for controlling of weed plants in sown farm crops involves using effective doses of preparations adapted for suppressing weed plants without affecting leguminous crops such as soya, feed beans, pea etc.

EFFECT: wider range of weed plant controlling means and processes.

5 cl, 2 dwg, 7 tbl, 13 ex

FIELD: organic chemistry, fungicides.

SUBSTANCE: invention describes substituted 1-(pyridinyl-2)-2-azolylethanols of the general formula (I): wherein R means hydrogen atom, direct or branched alkyl with 1 to 8 carbon atoms, cycloalkyl with from 3 to 8 carbon atoms; X means nitrogen atom or CH-group. Also, invention relates to a method for synthesis of these compounds and a fungicide composition that contains compound of the formula (I). Invention provides expanding assortment of fungicides for carrying out the effective control of harmful fungi.

EFFECT: valuable fungicide properties of compounds and composition.

5 cl, 1 tbl, 7 ex

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