Derivatives of amines or their salts and insecticidal composition based on them

 

(57) Abstract:

Usage: as insecticides. The inventive product - derived amine F.-ly (R1X)(R2)N-CR3-Z-R4where R1-pyridyl which may be substituted with halogen, C1-C4- -alkyl, galoidzamyescyennykh C1-C4the alkyl, optional galoidzamyescyennykh C1-C4- alkoxy, C1-C4- allylmercaptan, C1-C4- alkylsulfonyl, phenoxy, cyano, nitro, C1-C4- alkylaminocarbonyl, with the exception of unsubstituted 2-pyridyl, Persil, pyrazolyl, pyridazin or thiazolyl, which can be substituted C1-C4- alkyl or halogen; X is a straight or branched C1-C3- alkylen; R2-H, C1-C5- allylcarbamate, optionally substituted C1-C5- alkyl, C2-C5alkenyl, C2-C5- quinil, C3-C6- cyclooctyl, phenyl or the radical-Y-R5; Y IS O, SO2WITH or CO2, R5-H, optionally substituted C1-C5- -alkyl, C3-C6- cycloalkyl or optionally substituted phenyl; R3- H, optionally substituted C1-C5- alkyl, C2-C5alkenyl, C3-C8- ALK salt. Reagent 1: R1X(R2)-NH, where R1and R2above. Reagent 2: R3COCH2R4where R3and R4above. Reaction conditions: selection in free form or in salt form. 2 C. p. F.-ly, 4 PL.

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

For many years in the field of research of insecticides was developed and implemented in the practical use of a huge number of chemical products, such as organophosphorus insecticides, such as parathion and Malathion, and urethane insecticides, such as carbaryl and methomyl. These insecticides have played a very important role in improving agricultural production. However, in recent years some of these insecticides are under the control of environmental pollution caused by residue or buildup in nature, in addition, as a result of use over a long period of time is an infection of resistant insect pests. Therefore, it is necessary to develop new chemicals that have excellent insecticidally pests, and which can be used safely.

Known compound, which has no insecticidal activity

CH2-NHCl

(Boll. Chim. Farm, 1979 118/11/661-666).

The following compound is described in U.S. patent N 4918088, and has insecticidal activity

CH2-NHCH3< / BR>
However, this compound does not show insecticidal activity against lepidopteran insects and green rice of cycatki that are more serious pests of agricultural crops, although it detects activity against the cotton aphid.

The purpose of the invention to provide agricultural chemicals that can be successfully synthesized on an industrial scale, have a specific action and are safely applicable.

The proposed connection has a high insecticidal activity against lepidopteran and against polycrylic insects.

The present invention relates to compounds having the formula

R1-X-R3(I) where R1optionally substituted 5-6-membered aromatic heterokonta containing a nitrogen atom, with the exception of unsubstituted 2-pyridyl;

X optional salmenniemi, thiocarbamoyl, mono - or di-C1-C5-alkylthiomethyl, sulfamoyl, mono - or di-C1-C5-alkylsulfonyl, optionally substituted C1-C5-alkyl, optionally substituted C2-C5alkenyl, optionally substituted C2-C5-quinil, optionally substituted C3-C8-cycloalkyl, optionally substituted C3-C8-cycloalkenyl, optionally substituted aryl, or-Y-R5;

Y is O, S(O)n, CO, CS or CO2;

n is 0, 1 or 2;

R5hydrogen, optionally substituted C1-C5-alkyl, optionally substituted C2-C5alkenyl, optionally substituted C2-C5-quinil, optionally substituted C3-C8-cycloalkyl, optionally substituted C3-C8-cycloalkenyl or optionally substituted aryl;

R3hydrogen, optionally substituted C1-C5-alkyl, optionally substituted C2-C5alkenyl, optionally substituted C2-C5-quinil, optionally substituted C3-C8-cycloalkyl, or optionally substituted C3-C8-cycloalkenyl;

R4cyano or nitro;

Z is CH or N; or its salt.

Conn>/P>1. The method of obtaining 1:

- + RR4or R_____< / BR>
where r1and r2WITH1-C5-alkyl;

R1-R4and X have the specified values.

The reaction is carried out in an inactive organic solvent, preferably in an aromatic hydrocarbon solvent such as xylene, toluene or benzene, in the presence of an acid catalyst, such as n-toluensulfonate, if necessary while heating under reflux (under conditions of reflux distilled) (2). A method of obtaining a 2:

R

where r3WITH1-C5-alkyl;

R1-R3and X have the specified values.

This reaction is carried out in an inert organic solvent, preferably an alcohol, such as methanol, ethanol, at temperatures between room temperature and the boiling point of the used solvent.

3) the Method of obtaining 3:

OTHER3R1-X-R3< / BR>
where l halogen;

R1-R3and X have the specified values.

This reaction is carried out in an inert organic solvent, preferably DMF, THF, benzene, acetonitrile, acetone, methyl ethyl ketone, in the presence of an acid acceptor such as potassium carbonate, sodium hydride, is of 4:

+ Ral_____< / BR>
where R1-R3, X and Hal have the specified values. This reaction is carried out in the same manner as the reaction of the method of obtaining 3.

(5) the Method of obtaining 5:

RR3R1-X-

where R1-R3and X have the specified values.

This reaction is carried out in an inert organic solvent, preferably acetonitrile, tetrachloride hydrocarbon, ethylene dichloride, in the presence of a nitration reagent such as tetrafluoroborate nitronium between -20aboutC and the boiling point of the used solvent.

After the reaction is finished, the usual post-processing gives the target compound. The structure of the compounds of this invention was determined using tools such as IR, NMR, mass spectra and other

If R2the hydrogen in the compound of the present invention, there may be tautomers represented as

R1-X-OTHER3R1-X-NR3< / BR>
There may also be enantiomer, if Z N, and contradictory, if Z SN, presents

R1-X-R3R1-Z-R3< / BR>
The ratio varies depending on, for example, conditions of tools for analysis.

Sleduyuthem

CH2NH2+C2H5COCH2NO2____ CH2NH

In 50 ml of toluene were mixed to 4.2 g of 2-chloro-5-pyridylmethylamine, 3.5 g of 1-nitro-2-butanone and 0.1 g of n-toluensulfonate acid, the mixture was heated under reflux for 2 hours the Solvent is then drove away and the residue was purified using chromatography on a column of silica gel, giving 4.1 g of compound N 368, (PL. 1) so pl. 95-98aboutC.

P R I m m e R 2. 2-(2-Chloro-5-pyridylmethylamine)-1-cyano-1-propene

CH2NH2+CH3COCH2CN____ CH2NH

1.4 g of 2-chloro-5-pyridylmethylamine and 0.8 g of 1-cyano-2-propanol were mixed and the mixture was stirred at room temperature over night. The solvent is then distilled and the residue was purified using chromatography on a column of silica gel, giving 1.7 g of the compound N 528. (PL. 1). So pl. 95-98aboutC.

P R I m e R 3. N-Cyano-N-(2-chloro-5-pyridylmethyl)-N-methylacetamide

CH2NHCH3+C2H5O CHH3< / BR>
In 20 ml of methanol was mixed with 1.6 g of N-methyl-2-chloro-5-pyridylmethylamine and 1.2 g of ethyl-N-cyanoacetamide, the mixture was stirred at room temperature overnight. The solvent is then distilled and the residue was purified using chromatography on a column of silica gel, giving 1.8 g BR>
CH2NHH3+ C2H5I______ CHH3< / BR>
0.7 g sodium Hydride (purity 60% 0.7 g) was added to a solution of 3 g of N-cyano-N-(2-chloro-5-pyridylmethyl)acetamidine in 20 ml of N,N-dimethylformamide at the temperature of the ice bath. After stirring the mixture at the same temperature for 1 h, to the mixture was added 2.7 g iodine ethyl, followed by stirring for 5 h at room temperature. The reaction mixture was then poured into a mixture of ice water, extracted with ethyl acetate, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The obtained residue was purified using chromatography on a column of silica gel, giving 1.6 g of the compound No. 51 (PL. 1). So pl. 100-101aboutC.

P R I m e R 5. N-Cyano-N-(2-chloro-5-pyridylmethyl)-N'-methylacetamide

CH3NHH3+ ______ < / BR>
The sodium nitride (purity 60% 0.6 g) was added to a solution of 1.3 g of N-cyano-N'-methylacetamide in 20 ml of N,N-dimethyl - formamide at a temperature of an ice bath. After stirring the mixture at the same temperature for 1 h, to the mixture was added 2.2 g of 2-chloro-5-pyridylmethylamine, followed by stirring for 5 h at room temperature. The reaction mixture was then poured into a mixture of ice-water, extracted with ethyl acetate, dried OSU column chromatography on silica gel, giving 1.5 g of the compound No. 22 (PL. 1). So pl. 101-103aboutC.

Reference example. N-(2-chloro-5-pyridyl)-N-methylacetanilide

+< / BR>
To 40 ml of ethanol was added to 5.1 g of N-(2-chloro-5-pyridylmethyl)-N-methylamine, and then 4 g of the hydrochloride of ethylacetamide at 0aboutC. After stirring for one hour the reaction mixture was left to warmed to room temperature and stirred over night. The solvent is then distilled. The obtained white residue was washed with diethyl ether, giving of 7.3 g of the target compound. So pl. 192-197aboutC.

P R I m e R 6. N-(2-Chloro-5-pyridylmethyl)-N-methyl-N-nitroacetanilide

< / BR>
To a suspension of 1 g of N-(2-chloro-5-pyridylmethyl)-N-metilenhloride in 10 ml of dry acetonitrile was added dropwise 0.7 g V in nitrogen atmosphere at room temperature. After stirring for 30 min the solution was added dropwise to a suspension of 0.6 g of tetrafluoroborate nitronium in 5 ml of dry acetonitrile under nitrogen atmosphere while cooling with a mixture of ice water and left to mix for 4 hours then the mixture was poured into a mixture of ice-water, then extracted several times with chloroform. The combined chloroform layer was dried over magnesium sulfate, filtered of N 236 (PL. 1).ND251,5808.

Typical examples of the compounds of the present invention, including the compounds described above, are listed in table. 1.

The compounds of this invention show high insecticidal activity against a variety of insect pests such as Cutworm, cabbage moth, aphids, cycatki and delacey. In recent years, the reduction of the regulatory effect of organophosphorus and urethane insecticides, which is caused by the development of resistance to these insecticides has become a serious problem. In this situation, the development of new insecticides that are effective against resistant pests, very necessary. The compounds of this invention possess superior insecticidal activity against sensitive strains, but also against resistant organisms.

Insecticides, according to this invention contain as active ingredient one or more types of compounds expressed by the General formula (1). These active ingredients can be used such as they are received, but are usually used in the form of any of the forms characteristic of conventional agricultural chemicals, namely in the form of wettable powder, dust, EMU ready preparative forms. As additives and carriers used soy flour, wheat flour or other types of vegetable flour, diatomaceous earth, Apatite, gypsum, talc, pyrophyllite clay or other fine mineral powders, when necessary preparative solid form.

When you need preparative liquid form, then as solvents use kerosene, little mineral, oil, solvent naphtha, xylene, cyclohexane, cyclohexanone, dimethylformamide, dimethylsulfoxide, alcohol, acetone, water, etc. If you want, you can add surface-active agents in order to obtain a homogeneous and suitable preparative form. Wettable powders, emulsifiable concentrates, suspension concentrates, etc. thus obtained, diluted with water to obtain suspensions or emulsions of a given concentration, before they actually sprayed on plants in the field. Dusty or granules are applied directly without additional processing.

The compound of the present invention is effective, but they can be used by mixing with different types of insecticides, acaricides and fungicides.

Typical examples of acaricides and insecticides, which is alcidi (fungicides): Chlorobenzilate, chloropropyl, prolinol, bromopropylate, dicofol, dinobuton, binapacryl, Chlordimeform, amitraz, propargite, P.P.P.S., benoxinate, hexythiazox, terbutaline, polyactis, chinomethionat, teachings, chlorfenson, tetradifon, penprase, avermectins, clofentezine, flubendiamide, fenazaquin, pyridaben, fenpyroximate, florfenicol, thiophenemethyl, benomyl, thiram, iprobenfos, edifenphos, phtalic, provenzal, isopropyl, CHLOROTHALONIL, Captan, polyoxin-In, blasticidin-S, kasugamycin, validamycin, tricyclazole, pyroxylin, finaince, mepronil, flutolanil, pencycuron, iprodion, hymexazol, metalaxyl, triflumizole, declomycin, telital, vinclozolin, procymidone, bitertanol, triadimefon, prochloraz, pirivenas, fenarimol, fenpropimorph, triforine, metalaxyl, oxycarboxin, perinatal, declomycin, fluazinam, oxadixyl, ethanolic, TRTN, propamocarb, fosetyl, dihydrostreptomycin, anilazine, dithianon, dietphenterm.

Insecticide (acaricide): organophosphorus and urethane type; for example, fenthion, fenitrothion, diazinon, chloropyrifos, oxidation, amidation, pentat, dimethoat, formation, Malathion, trichlorfon, thiometon, phosmet, Manson, dichlorvos, Arafat, ERVR, dialifos, parathionmethyl, oxydemetonmethyl, the carbofuran, benfuracarb, metolcarb, carbaryl, primicarb, ethiofencarb, fenoxycarb.

Insecticide (acaricide) PYRETHROID type: permethrin, cypermethrin, deltamethrin, fenvalerate, fenpropathrin, pyrethrins, allethrin, tetramethrin, resmethrin, Partin, demetrin, proproten, bifenthrin, protran, fluvalinate, cyfluthrin, cigalotrin, flucythrinate, etofenprox, cicloprofen, tralomethrin, silanion.

Insecticides benzoylferrocene type and other types: diflubenzuron, chlorfluazuron, triflumuron, diflubenzuron, buprofezin, pyriproxyfen, flufenoxuron, engine oil.

Below are some examples of preparative forms. Media surface-active agents, etc. which are added, are not limited to these examples.

P R I m e R 7. Emulsifiable concentrate, including

The compound of the present invention 10 Alkylphenolethoxylates 5 Dimethylformamide 50 Xylene 35

The components are mixed and dissolved. For use when spraying or spraying the liquid mixture is diluted with water to obtain an emulsion.

P R I m e R 8. Wettable powder, including

The compound of the present invention 20

Ester of sulfuric acid and higher tonkodispersnoe powder, which to use by spraying diluted with water to form a suspension.

P R I m e R 9: dust, h:

The compound of the present invention 5 Talc 94.7 silicon Dioxide 0,3

These ingredients are mixed and pulverized, used in powdered form when spraying.

P R I m e R 10. Granules, including

The compound of the present invention 5 Clay 73 Bentonite 20

Dioctylsulfosuccinate sodium 1 sodium Phosphate 1

These compounds granularity and apply when using these as they are.

Industrial applicability.

The following tests show insecticidal activity of the compounds of this invention.

And with n s t a n d s 1. Efficacy against cotton aphid.

Was inoculable 30-50 insects of cotton aphid on plot (tray) using a small brush on the leaves of cucumbers, which were sown in trays, 10 cm in diameter, age 10 days. after germination. Through the day the affected insect pests (injured) was removed, sprayed a chemical solution, which is prepared so that the emulsifiable concentrate described in example 7 was diluted with water to the concentration of the compound 125 ppm million counts the number of live pests, the efficiency of the control or destruction was calculated in comparison with a case of unhandled tray. The results are shown in table. 2.

And with n s t a n d s 2. Effectiveness against green rice of cycatki.

Seedlings of rice in the age after emergence 7 days. immersed in a chemical solution, which is prepared so that the emulsifiable concentrate insecticide described in example 7 was diluted with water to the concentration of the compound 125 frequent. /million at 30 C. After drying in air, the treated seedlings were placed in the experimental tube and inoculable 10 insect larvae 3rd age stage of green rice cycatki resistant to organophosphorus and urethane insecticides. Tubes were covered with gas cloth and placed in a thermostat with a temperature of 25aboutC and humidity 65% After 5 days. tested mortality.

The results are shown in table. 3.

And with n s t a n d s 3. Efficacy against rice scoops.

Compound was converted to the preparative form of wettable powder in the same manner as in example 8. Compounds were diluted with water to a concentration of 125 ppm million Sheets of corn was immersed in a chemical solution at 30 C. After air drying processed if the above glass lids and placed in a thermostat with a temperature of 25aboutC and relative humidity 65% Mortality was checked after 5 days. Each experiment was repeated twice. The results are shown in table. 4.

1. Derivatives amine of General formula

< / BR>
where R1pyridyl which may be substituted with halogen, C1- C4-alkyl, halogen-substituted C1C4-alkyl, C1- C4-alkoxy, C1C4-allylmercaptan, C1- C4-alkylsulfonyl, phenoxy, cyano, CI-C1- C4-alkylaminocarbonyl, with the exception of unsubstituted 2-pyridyl, Persil, pyrazolyl, pyridazin or thiazolyl, which can be substituted C1- C4-alkyl or halogen;

X straight or branched C1C3-alkylen;

R2hydrogen, CI-C1C5-allylcarbamate, optionally substituted C1C5-alkyl, C2C5alkenyl, C2- C5-quinil, C3C6-cycloalkyl, phenyl or a radical Y - R5where Y is O, SO2, CO or CO2and R5hydrogen, optionally substituted C1C5-alkyl, C3- C6-cycloalkyl or halogen-substituted phenyl;

R3hydrogen, optionally substituted C1C5-alkyl or C3C6-cycloalkyl;

R4cyanigosa ingredient derived amine and targeted supplements, characterized in that as the amine derivative is used as a compound of General formula

< / BR>
where R1pyridyl which may be substituted with halogen, C1- C4-alkyl, halogen-substituted C1C4-alkyl, C1- C4-alkoxy, C1C4-allylmercaptan, C1- C4-alkylsulfonyl, phenoxy, cyano, CI-C1- C4-alkylaminocarbonyl, with the exception of unsubstituted 2-pyridyl, Persil, pyrazolyl, pyridazin or thiazolyl, which can be substituted C1- C4-alkyl or halogen;

X straight or branched C1C3-alkylen;

R2hydrogen, CI-C1C5-allylcarbamate, optionally substituted C1C5-alkyl, C2C5alkenyl, C2- C5-quinil, C3C6-cycloalkyl, phenyl or a radical Y - R5where Y is O, SO2, CO or CO2and R5hydrogen, optionally substituted C1C5-alkyl, C3C6-cycloalkyl or halogen-substituted phenyl;

R3hydrogen, optionally substituted C1C5-alkyl or C3C6-cycloalkyl;

R4cyano or nitro;

Z is CH or N,

or their salts in an amount of 5 to 20 wt. target additives else.

 

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