Derivatives of 2-substituted phenyl-2-oxazoline or 2 - substituted phenyl-2-thiazoline and insecticidal and/or acaricidal composition based on them


C07D277/10 - with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
C07D263/10 - with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms

 

(57) Abstract:

The essence of the invention: derivatives of 2-substituted phenyl-2-oxazoline or 2-substituted phenyl-2-thiazoline General formula 1 given in the description, where Z is oxygen atom or sulfur, And is a direct link or lowest Allenova group. Acaricide and/or insecticida composition contains 0.01 - 80,00 wt.% derivatives of 2-substituted phenyl-2-oxazoline or 2-substituted phenyl-2-thiazoline formula 1 and an adjuvant. 2 S. and 9 C.p. f-crystals, 7 PL.

The invention relates to derivatives of 2-substituted phenyl-2-oxazoline or thiazoline, which are new compounds, containing insecticides or acaricidal as an effective component.

Known methods for producing certain types of compounds 2,4-diphenyl-2-oxa - or triazoline (Tetrahedron Lettess, T. 22 N 45, S. 4471-4474, 1981, Chemical Abstracts, T. 98, No. 19, K, 1983, Journal of Organic chemictry, T. 52, S. 2523-2540, 1987.

A method of obtaining2N-heterocyclic compounds [1], used as intermediates to obtain the effective components in drugs or compounds as those having biological activity, for the treatment of diabetes.

However, TP is s not found.

Description of the efficiency of some derivatives of 2-amino-2-oxazoline against mites (Acarina) or aphids found in Pesticide Biochemistry and discrimination, T. 30, S. 190-197, 1988.

Known derivatives of 2,4-substituted 2-oxa - or triazoline having insecticidal and acaricidal activity [2].

Were improved new insecticidal and acaricidal tools to create compounds with insecticidal activity against insect pests in a wide range of low toxicity.

Parasitic on plants harmful insects and mites cause, as you know, serious damage to the useful plants, such as cereals, including rice, wheat, etc., legumes, including soybean, beans, fiery-red, and so on, various fruit trees, including apples, oranges, pear trees, etc. , vegetable plants, including eggplant, cucumbers, strawberries, etc., flower plants, including roses, carnations and so on, tea plants and so on Many kinds of insecticides and/or acaricides currently used in practice.

However, in recent years, a serious problem arose in connection with the acquisition of resistance (or tolerance) of parasi - exporting plants harmful insects or lesbina problem in cases of repeated use of the same types of medicines. To avoid such manifestations of resistance to medicines, consistent replaced by new types of insecticides and/or acaricides to avoid re-use of identical medicines and combination use of drugs with different mechanism of action.

Derivatives of 2-amino-2-oxazoline [3] - type compounds among the derivatives of 2-oxazoline possess insecticidal or acaricidal activity, characterized by soderhjelm amino group at the 2nd position oxazolinone kernel and provide activity against mites or aphids.

Derivatives of 2-oxazoline [2], disubstituted in the 2,4-position have activity against Clasica spider in the stage of the testicles and insecticidal activity against aphids, green cicadas rice or brown cicadas rice.

The objective of the invention is the creation of derivatives of 2-substituted phenyl-2-oxa or thiazoline, which are new compounds exhibiting a pronounced effect against harmful insects or mites in a wide range, but has low toxicity.

Derivatives of 2-substituted phenyl-2-oxa - or thiazolin represented by the General formula

A (1) where R1and R2SCHOU alkoxygroup, the nitrogroup, lower haloalkyl group or a lower haloalkoxy provided that R1and R2at the same time not predstavlyaet a hydrogen atoms; R3is a hydrogen atom, halogen atom, lower alkyl group or lower alkoxygroup; R4is an alkyl group having seven or more atoms of hydrogen, allylthiourea, lower alkoxy-lower alkyl group, lower alkoxy-lower alkoxygroup, alkenylacyl having three or more carbon atoms, lower alkyloxy, three (lower alkyl)-silyl group, cycloalkyl group which may be substituted by a lower alkyl group, or a group represented by the formula

B where a is a direct bond, an oxygen atom, lower Allenova group, lower accelerograph or di-(lower alkyl)-Sealy - supplemented flax group; Q is CH or a nitrogen atom; n is zero or an integer from 1 to 5; each R5is a halogen atom, an alkyl group, alkoxygroup, lower haloalkyl group, lower haloalkoxy or tri-(lower alkyl)-silyl group, if n is greater than one, of the radicals R5may be the same or different; And a is a direct bond or lower Allenova group; Z is an oxygen atom or a sulfur atom.

The term "lower" means that uchet fluorine atom, chlorine, bromine and iodine.

The alkyl group may be either in the form of linear or branched chains and may be represented by alkyl groups having 1-20 carbon atoms, preferably 1-15 carbon atoms, including methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isoamyl, neopentyl, n-hexyl, n-Gentil, 1,1-dimethylpentyl, n-octyl, 1-methylheptan, 1,1-dimethylheptyl, 1,1-dimethyl-4-methylpentyl, n-nonyl, n-decyl, 4,8-dimethylene, n-undecyl, 1-pentylhexyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-octadecyl, n-Needell, n-akosile group, etc.

Alkoxygroup and allylthiourea - (alkyl)-0-group, and (alkyl)-S-group in which alkyl has the specified values.

Gataullina group is an alkyl group in which at least one of the hydrogen atoms connected to carbon atoms in the alkyl group substituted by a halogen atom, and specifically include chloromethyl, trifluoromethyl, foradil, triptorelin, perforation group, etc. Haloalkoxy - (haloalkyl)-0-group, in which haloalkaline part has a specified value, such as tripterocarpa etc.

The term lower alkoxy-lower alcatena, defined previously, for example ethoxymethylene, n-propoxymethyl, isoprop - cimetidina, n-butoxymethyl, isobutoxyethene, 2-methoxyaniline, 2-ethoxyethylene group, etc.

Lower alkoxy-lower alkoxygroup means (lower alkyl)-0-(lower alkyl)-0-group, which includes, for example, 2-methoxyethoxy, 2-ethoxyethoxy, 2-n-Pro - maxitaxi, 4-isopropoxyphenoxy etc.

Alkenylacyl - (alkenyl)-0-group, in which Alchemilla part is alkenylphenol group in the form of a linear chain or branched chain and is represented by alkenylacyl having 3-15 carbon atoms, including allyloxy, butenyloxy-, 3-methyl-2-butenyloxy-, TRANS - 3,7-dimethyl-2,6-octadienal, farnesylated, citronellate etc.

Lowest alkyloxy represented by propargyloxy etc.

The term tri-(lower alkyl)-silyl group means, for example, trimethylsilyloxy, ethyldimethylamine, n-propyltrimethoxysilane, tert-butultimately - silyl, triethylsilyl, methyldiethylamine group, etc.

Cycloalkyl group includes a group having 3-8 carbon atoms, such as tsiklogeksilnogo group, and cycloalkyl groups which include methylcyclohexanol, ethylcyclohexyl, tert-butylcyclohexyl group, etc.

Lower Allenova group can be either in the form of a straight chain or branched chain, and examples are as follows: -CH2,-CH2-CH2-,-,-CH2-CH2-CH2- ,- CH2-CH2-CH2-CH2-, -CH2-CH2, -CH--CH2and so on

Lowest accelerograph and lower alkylenedioxy each mean-0-(lower alkylenes)-group, and-0-(lower alkylene)-0-group, respectively, in which the lower Allenova part has a given value.

Di-(lower alkyl)-silyl group is represented

- ,- - , and so on

Each of the symbols R1and R2in the General formula (1) is the same or different, preferably a hydrogen atom, halogen atom, methyl group, methoxy group, triptorelin group or tripterocarpa provided that R1and R2are not simultaneously a hydrogen atom. Substituting atom or group should be preferably in the 2, 4 or 6-position in the benzene nucleus. In particular, the cases in which each of R1and R2represents a halogen atom, preferably a fluorine atom or a chlorine atom is most favorable.

R
B where - a direct link an oxygen atom, a group-CH2- or-och2- ;- CH or a nitrogen atom; n is zero or an integer from 1 to 5; R51is a halogen atom, an alkyl group or alkoxygroup, if n is greater than one, of the radicals R51may be the same or different; And a is a direct bond; Z is preferably an oxygen atom.

In the formula (1) class of preferred compounds is 2-substituted phenyl-2-oxazoline represented by the General formula

(1-a) where R11and R21- same or different and each represents a halogen atom; R3and R4have the specified values.

Among the classes more preferred compounds of the compounds of the formula (1-a) can be listed derivatives of 2-substituted phenyl-2-oxazoline, presents any of the following formulas

(alkylalkyl)(1-b)

(1-c)

(1-d)

(1-e)

(1-f)

In each of the above formulas, R51represents a halogen atom, alkyl group, or alkoxygroup, if n is greater than one, of the radicals R51may be the same or different; each R11, R21, R3, Q and n have the specified values.

Joined the General formula COOH (2) where each of R1and R2have the same meanings as defined above,

with aminosterol General formula

ACHOH (3)

or formulas

ACHNH2(4) where each R3, R4and have these znaczenia,

b) processing the derived amidopirina represented by the General formula

CONH (5)

or formula

CONHCHA (6) where each R1, R2, R3, R4and have the same meaning as defined above, dehydrating agent;

C) treating compound represented by the General formula

CONH (7) where each of R1, R2, R3, R4and a have the above meanings; W is a halogen atom, alkylsulfonate, such as Matinal - philokyprou, or arylsulfonate, such as a pair of toluensulfonate, basis.

The reaction of the compound benzoic acid of the formula (2) with a derivative of amerosport formula (3) or (4) by the method (a) can usually be carried out in a suitable solvent such as an aromatic hydrocarbon solvent include benzene, toluene, xylene, nitrobenzene, chlorobenzene, dichlorobenzene, etc., at a temperature of from 70aboutC to the boiling point of the solvent and dehydrating agent.

Dehydrating agent, ispara, dicyclohexylcarbodiimide, paternity phosphorus, etc., the Compound of formula (1), where Z is an oxygen atom, are obtained when using a dehydrating agent such as sulfuric acid, polyphosphoric acid, pathiakis phosphorus, dicyclohexylcarbodiimide, etc. and the compound of formula (1) where Z is a sulfur atom, obtained when using a dehydrating agent such as paternity phosphorus, etc.

The molar ratio of compounds of formula (2) derived amerosport formula (3) or (4) in the reaction should not be strictly limited, but is preferably derived amerosport formula (3) or (4) must be used in a quantity of 0.8 to 1.2 mol per one mol of the compounds of formula (2). Thus, the amount specified dehydrating, use - used in the reaction, not goldino to be strictly limited, but preferably it should be in the range of 2-8 mol for one mol of the compounds of formula (2).

Processing the derived amidopirina formula (5) or (6) dehydrating agent according to the method b) can be carried out under the conditions of method a).

Derivatives of amide alcohol of formula (5) or (6), used as starting material in method (b) can be obtained usaimage the ID, including the acid chloride, bromohydrin, etc. derived amerosport formula (3) or (4) in the presence of a base.

The reaction is usually conducted in a solvent. Solvents can be water, alcohol such as methanol, ethanol, etc., ethers such as diethyl ether, tetrahydrofuran, dioxane, diglyme, etc., aromatic hydrocarbons such as benzene, toluene, xylene and so on, halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, dichloroethane, etc., a Suitable reaction temperature is in the range from 0 to 50aboutWith in General.

The necessary basis can be represented by inorganic bases such as sodium hydroxide, potassium hydroxide, potassium carbonate, etc., organic tertiary bases, such as triethylamine, N,N-dimethylaniline, pyridine, 4-N,N-dimethylaminopyridine etc.

In this reaction the molar ratio of the reactive derivative of the compound of the formula (2) derived amerosport formula (3) or (4) is not particularly limited, but derived amerosport formula (3) or (4) is preferably used in a molar ratio of 0.8 to 1.2 mol per one mol of the reactive derivative of compound f the th compounds of formula (2) is deemed appropriate.

The compound of formula (7) in the above reaction) can be obtained by the coupling of compounds of formula (5), used as starting material in the above reaction (b), with halogenation agent or sulfurous agent.

The reaction halogenization or sulfonation in this case is usually conducted in a solvent.

Examples of useful solvents for the reaction are aromatic hydrocarbons such as benzene, toluene, xylene and so on, halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, dichloroethane, etc., and ethers such as diethyl ether, tetrahydrofuran, dioxane, diglyme, etc., Examples of useful galogenidami agents include chloride thionyl, bromide tional, phosphorus oxychloride, phosphorus trichloride, tribromide phosphorus, etc. Useful sulfurous tool can be chloride methanesulfonyl, chloride para-toluensulfonyl etc.

The necessary reaction temperature in this case is usually in the range of 0aboutC to the boiling point of the solvent.

Attitude halogenides agent or sulfurous agent used in the reaction, the compound of formula (5) is also strictly mol for one mol of the compounds of formula (5) is acceptable.

The interaction of the compounds of the formula (7) to form a cyclic structure with the base advantageously carried out in a solvent including water and alcohols, such as methanol, ethanol, etc. at a temperature in the range from 40 to 100aboutWith as usual. Inorganic bases mentioned for the reaction b), are suitable bases, and their amount to be used is 1 to 6 equivalents per one mole of the compounds of formula (7).

The compounds of formula (1) received any of the reactions a), b) and C) can be isolated and purified by the known methods such as column chromatography, recrystallization, etc.

The solvent for column chromatography and recrystallization should be selected among, for example, benzene, methyl alcohol, ethyl alcohol, chloroform, n-hexane, ethyl acetate, etc. and mixtures containing these solvents.

These compounds according to the invention is further specifically explained with reference to the following examples of synthesis.

P R I m e R 1. Synthesis of 2-(2,6-differenl)-4-(4-n-decyloxybenzoic)-2-oxazoline.

To a mixture of 2.93 g (10 mmol) 2-amino-2-(4-n-decyloxybenzoic)-ethanol, 1.01 g (10 mmol) of tryptamine and 30 ml tetrahedra the temperature of an ice bath was added a solution of 1.77 g (10 mmol) of 2,6-differentiald in 15 ml of tetrahydrofuran. After further stirring for 3 h at room temperature the formed triethylamine hydrochloride was removed by filtration using a glass filter, and the filtrate was concentrated under reduced pressure. To the concentrate was added 50 ml of toluene and 2,84 g (20 mmol) of phosphorus pentoxide and then was heated under reflux for 3 h on an oil bath. The reaction mixture is then washed with 50 ml of 10% aqueous aqueous solution of sodium hydroxide and then saturated aqueous sodium chloride after cooling to room temperature, followed by drying over anhydrous sodium sulfate and concentration under reduced pressure. This concentrate was purified by chromatography on a column of silica gel using a mixture solvent of n-hexane-ethyl acetate in the ratio of 8:2 as the mobile phase and obtained 2-(2,6-differenl)-4-(4-n-decyloxybenzoic)-2-OK - Catlin (compound No. 94, shown in table.1.).

Pale yellow liquid, nD25= 1,5236, yield 2.15 g (51,8%). An NMR spectrum on nuclei1H (CDCl3TMS (million share): from 0.90 (3H, t, J = 6 Hz), 1,1-2,1 (N, m), of 3.95 (2H, t, J = 6 Hz), 4,30 (1H, t, J = 8 Hz), to 4.87 (1H, t, J = 8 Hz), to 5.85 (1H, t, J = 8 Hz), and 7.1 to 7.9 (7H, m).

Range IR (KBr, max in cm-1): 2810-3135 (C-H), 1670 C 2,43 g (10 mmol) 2-amino-2-(3-phenyl-4-methoxyphenyl)-ethanol, 1.01 g (10 mmol) of triethylamine and 30 ml of tetrahydrofuran contained in Balaenoptera (spheroidal) flask (100 ml) for 30 min under stirring at the temperature of an ice bath was added of 1.93 g (10 mmol) chloride 2-chloro-6-Fiorentina in 15 ml of tetrahydrofuran. After further stirring for 3 h at room temperature the resulting triethylamine hydrochloride was removed by filtration using a glass filter and the filtrate was concentrated under reduced pressure. To this concentrate, diluted with 30 ml of benzene in baklazhanovyuyu flask (100 ml), added value of 4.76 g (40 mmol) of chloride tiomila one portion and heated under reflux for 3 h under stirring on an oil bath. The reaction mixture was cooled to room temperature and the benzene and excess chloride tiomila evaporated under reduced pressure. Then to the residue was added 30 ml of methanol and 5 ml of 30% aqueous solution of sodium hydroxide, followed by stirring for 20 min at 70aboutC in an oil bath and then concentrated under reduced pressure. The concentrate was diluted with 100 ml of benzene and washed with saturated aqueous sodium chloride, dried over anhydrous sodium sulfate and then contentlist solvent mixture n-hexane-ethyl acetate in the ratio of 8:2 as the mobile phase and obtained 2-(2-chloro-6-forfinal)-4-(3-phenyl-4-methoxyphenyl)-2-oxazoline (compound No. 147) in the form of a pale yellow liquid, so Kip. 82aboutWith the release of 1.8 g (47,4%).

1H-NMR spectrum (CDCl3, TMS, million share): to 3.73 (3H, s), 4,30 (1H, t, J = 9 Hz), 4,82 (1H, t, J = 9 Hz), of 5.48 (1H, t, J = 9 Hz), 6,80-7,7 (11N, m).

IR spectrum (KBr, max in cm-1): 2800-3150 (C-H), 1664 (C=N).

P R I m e R 3. Synthesis of 2-(2,6-differenl)-4-(4-n-decipher)-2-oxazoline.

To the mixture 2,77 g (10 mmol) 2-amino-2-(4-n-decipher)-ethanol, 1.01 g (10 mmol) of triethylamine and 30 ml of tetrahydrofuran contained in baklazhanovyuyu (spheroidal) flask (100 ml) was added over 30 minutes while stirring and cooling in an ice bath to 1.77 g (10 mmol) of 2,6-differentiald in 15 ml of tetrahydrofuran. After further stirring for 3 h at room temperature the resulting triethylamine hydrochloride was removed by filtration using a glass filter, and the filtrate was concentrated under reduced pressure. This concentrate was diluted with 50 ml of benzene and 3.57 g (30 mmol) of chloride tiomila and then was heated under reflux for 3 h with stirring on an oil bath. The reaction mixture was concentrated under reduced pressure and diluted with 50 ml of methanol, followed by adding dropwise 2 ml of a 50% aqueous solution of sodium hydroxide at 60aboutWith stirring. After dalnas the relevant drying over anhydrous sodium sulfate and concentration under reduced pressure. This concentrate was purified by chromatography on a column of silica gel, using as mobile phase solvent mixture n-hexane-ethyl acetate 8:2 ratio, and obtained 2-(2,6-differenl)-4-(4-n-decipher)-2-oxazoline (compound No. 20) in the form of a pale yellow liquid, nD25= 1,5241, yield 3.4 g (to 85.2%).

Range1H-NMR (CDCl3, TMS, million share): from 0.90 (3H, t, J = 6 Hz), 1,1-2,0 (1H, m) to 2.66 (2H, t, J = 7 Hz), 4,33 (1H, t, J = 8 Hz), to 4.87 (1H, t, J = 8 Hz), of 5.50 (1H, t, J = 8 Hz), 6,8-in 7.7 (7H, m).

IR spectrum (KBr, max in cm-1): 2856-2928 (C-H), 1668 (C=N).

P R I m e R 4. Synthesis of 2-(2-chloro-6-forfinal)-5-(4-n-octyloxyphenyl)-2-thiazoline.

To a mixture of 2.65 g (10 mmol) 2-amino-1-(4-n-octyloxyphenyl)-ethanol, 1.01 g (10 mmol) of triethylamine and 30 ml of tetrahydrofuran contained in baklazhanovyuyu (spheroidal) flask (100 ml) was added a solution of 1.93 g (10 mmol) chloride 2-chloro-6-fervently in 10 ml of tetrahydrofuran over 30 minutes with stirring at a temperature of an ice bath. After further stirring for 3 h at room temperature the formed triethylamine hydrochloride was removed by filtration using a glass filter, and the filtrate was concentrated under reduced pressure. To this concentrate and 30 ml of toluene contained in the decrees 4 h at an oil bath with stirring. After cooling to room temperature the reaction mixture was diluted with 40 ml of 30% aqueous solution of sodium hydroxide and stirred at room temperature for one hour. In the reaction mixture were added 100 ml of benzene, washed with saturated aqueous sodium chloride followed by drying over anhydrous sodium sulfate and concentrated under reduced pressure. This concentrate was purified by chromatography on a column of silica gel, using as mobile phase solvent mixture n-hexane-ethyl acetate 8:2 ratio, and obtained 2-(2-chloro-6-forfinal)-5-(4-n-octyloxyphenyl)-2-thiazoline (compound N 91) in the form of a pale yellow liquid, so Kip. 41,0-41,5aboutWith the output 3,20 g (76,2%).

Range1H-NMR (CDCl3, TMS, million share): of 0.87 (3H, t, J = 6 Hz), 1,10-2,03 (N, m), 3,93 (2H, t, J = 6 Hz), 4,70 (2H, DD), to 5.17 (1H, t, J = 7 Hz), 6,77-7,47 (7H, m).

IR spectrum (KBr, max in cm-1): 2800-3150 (C-H), 1620 (C=N).

P R I m e R 5. Synthesis of 2-(2,6-differenl)-4-(4-n-octylphenyl)-2-oxazoline.

To the mixture 2,49 g (10 mmol) 2-amino-2-(4-n-octylphenyl)ethanol, 1.01 g (10 mmol) of triethylamine and 30 ml of tetrahydrofuran over 30 minutes with stirring at a temperature of an ice bath was added a solution of 1.77 g (10 mmol) chloride 2,6-differentail in 15 ml tefillat concentrated under reduced pressure. Mix this concentrate, 30 ml of benzene and 3.57 g (30 mmol) of chloride tiomila was heated under reflux for 3 h on an oil bath. The reaction mixture was cooled to room temperature and concentrated under reduced pressure. The concentrate was diluted with 30 ml of methanol, followed by addition of 4 ml of 30% aqueous solution of sodium hydroxide for 10 min at 70aboutWith stirring. After this, continuing the stirring at 70aboutC for 20 min and cooled again to room temperature, reational the mixture was extracted with ethyl acetate, washed with saturated aqueous sodium chloride, dried over anhydrous sodium sulfate and concentrated under reduced pressure. This concentrate was purified by chromatography on a column of silica gel, using as mobile phase solvent mixture n-hexane-ethyl acetate 8: 2 ratio, and obtained 2-(2,6-differenl)-4-(4-n-octylphenyl)-2-oxazoline (compound No. 6) in the form of a colorless oily substance, nD25= 1,5226, yield 3.1 g (83.6 percent).

1H-NMR spectrum (CDCl3, TMS, million share): 0,56-1,73 (15 NM, m) 2,60 (2H, t, J = 8 Hz), 4,20 (1H, t, J = 8 Hz), 4,70 (1H, t, J = 8 Hz), lower than the 5.37 (1H, DD, J = 8 Hz, 10 Hz), 6.73 x-EUR 7.57 (7H, m).

IR spectrum (KBr, max in cm-1): 1670 (C=C of 3.12 g (10 mmol) 2-amino-2-[4-(2,4-dichloraniline)-phenyl]-ethanol, 1.01 g (10 mmol) of triethylamine and 30 ml of tetrahydrofuran was added over 30 min with stirring at the temperature of the ice bath a solution of 1.77 g (10 mmol) chloride 2,6-differentail in 15 ml of tetrahydro - furan. After continued stirring at room temperature for 3 h, the reaction mixture was filtered and the filtrate was concentrated under reduced pressure. To this concentrate was added 30 ml of tetrahydrofuran, 1.01 g (10 mmol) of triethylamine, and 1.15 g (10 mmol) chloride methanesulfonyl dissolved in 15 ml of tetrahydrofuran over 30 minutes with stirring at a temperature of an ice bath.

After further stirring for 3 h at room temperature the reaction mixture was filtered and the filtrate was concentrated under reduced pressure. To this concentrate was added 50 ml of methanol and 1.0 g (15 mmol) of 85% potassium hydroxide and stirred 2 h at 70aboutC. After cooling again to room temperature, the reaction mixture was extracted with ethyl acetate, washed with saturated aqueous sodium chloride, dried over anhydrous sodium sulfate and concentrated under reduced pressure. This concentrate was purified by chromatography on silica gel using a solvent mixture of n-hexanet) in the form of colorless crystals, so pl. 104,0-104,5aboutWith the release of 3.5 g (80,6%).

Range1H-NMR (CDCl3, TMS, million share): 4,30 (1H, t, J = 9 Hz), a 4.83 (1H, t, J = 9 Hz), to 5.17 (2H, s), of 5.50 (1H, t, J = 9 Hz), 6-80-7,75 (10H, m).

IR spectrum (KBr, max in cm-1): 1670 (C=N).

P R I m e R 7. Synthesis of 2-(2,6-differenl)-4-(2-fluoro-n-nonylphenyl)-2-oxazoline.

To a mixture of 2.81 g (10 mmol) 2-amino-2-(2-fluoro-4-n-nonylphenyl)-ethanol, 1.77 g (10 mmol) of 2,6-diferential acid and 20 ml of toluene was added 3 g (30 mmol) of concentrated sulfuric acid and heated for 7 hours under reflux with stirring. After cooling to room temperature the reaction mixture is successively washed with 30 ml of 10% aqueous sodium hydroxide solution and then 30 ml of a saturated solution of sodium chloride, dried over anhydrous sodium sulfate and concentrated under reduced pressure. This concentrate was purified by chromatography on a column of silica gel using a mixture solvent of n-hexane-ethyl acetate 8: 2 ratio, and obtained 2-(2,6-differenl)-4-(2-fluoro-4-n-nonylphenyl)-2-oxazoline (compound No. 42) as a pale brown oily substance, nD25= 1,5184, the output of 2.27 (66,2%).

Range1H-NMR (CDCl3, TMS, million share): 0,7-1,9 (17H, m) to 2.65 (2H, t, J = 8 Hz), or 4.31 (1H, SS="ptx2">

Other compounds listed in the table.1, were synthesized by methods similar to those described in examples 1-7.

Physical data in the table show the refractive index (nD25) except those marked with a star coy, which show the melting point (aboutC).

In table. 1 used with the following elements: IU - methyl, Bu is butyl Et - ethyl Pen - Pentel Pr - propyl Neh - hexyl

Compounds of General formula (1), provided by the present invention exhibit high ovicidal, insecticide - ing and acaricidal activity against insects and/or mites, harmful for agriculture, horticulture, and/or to prevent epidemics, with insignificant toxicity to useful crops. Thus, they are useful as active ingredients of insecticides or acaricides for agriculture, horticulture and/or to prevent epidemics.

The compounds of formula (1) have excellent regulatory effectiveness against insects and mites, which are harmful to useful cultivated plants, and/or the ability to prevent epidemics. These insects include, for example, aphids such as Myzus persicae, Aphis gossypii, Lipaphis crysimi, Aphis citricola, Hippolachnus piri and so is AK Hezara antemrata, Cletus punetiger, Riptortus clavatus, etc., thrips, such as Scirtothrips dorsalis, Thripspalmi, Ponticulothrips diospyrosi etc., harmful insects from the order Orthoptera, such as Orya gezoensis, Lcustroi migratoria, etc., harmful insects from the order Coleoptera, such as Anomala cuprea, Onlema eryzae, Epilachusa Vigintioctomaculota etc., harmful insects of the order Diptera such as Musca domestica, Calexpipiens etc., harmful insects from the order Lepidoptera, such as Plutella xylostella, spodoptera litura, Chilo sappressalis etc., and ticks such as Tetranychus urticoel, Tetranuychus cinnabarinus, Tetranychus kanzawai, Panonychus ulmi, Panonychus citri, etc.

Consequently, the active compounds of the formula (1) is useful as an effective ingredient in insecticides or acaricides for agriculture, horticulture and/or prevention of epidemics.

In the practical use of these compounds as an active ingredient for insecticides or acaricides compound of formula (1) can be one or a combination of two or more kinds of compounds and can be prepared in various forms of preparations are acceptable for agricultural or horticultural use and preventing epidemics optionally in combination with other auxiliary agent. Useful AIDS for the preparation of the forms of the drugs does not necessarily include, the preparation of the forms of medications, depending on the requirements of the situation.

Carriers or diluents contain solid or liquid form, for example mineral powders or granules, of substances such as diatomaceous earth, talc, clay, alumina, kaolin, montmorillonite, silicic acid, amorphous silica, etc., and powders of plant or animal origin, such as starch powder, soy cultural, flour powder, fish meal, etc., as a solid media type - water, alcohols, including methanol, ethylene glycol, Phenoxyethanol, etc., ketones, including acetone, methyl ethyl ketone, etc., aromatic hydrocarbons, including xylene, trimethylbenzene, methylnaphthalene, solvent-naphtha, etc., aliphatic hydrocarbons, including hexane, cyclohexane, kerosene, light oil, etc., ethers, including dekozan, diisopropyl ether, tetrahydrofuran, etc., gazogeneratornyj hydrocarbons, including dichloromethane, trichloroethane, etc., amides including dimethylformamide, etc., NITRILES including acetonitrile, etc., sulfur compounds, including dimethyl sulfoxide, etc., vegetable oils, including soybean oil, olive oil, etc., and so on

Useful surfactants include, for example, surfactants of the nonionic type, such as simple alkyloxyalkyl, esters of fatty acids polyoxyethylenesorbitan etc., and surfactants of the anionic type, such as salts of esters of alkylarylsulfonates, esters of polyoxyethylenesorbitan, etc. and mixtures thereof.

Dispersing means or binder, for example, salts of ligninsulfonate, condensate formal - degidi and naphthalenesulfonate, salt of alginic acid, starch, derivatives of cellulose, montmorillonite, synthetic water-soluble polymers, synthetic resins, etc.

Stabilizers are, for example, esters of phosphoric acid, glycols, nonionic surfactants, aromatic diamines, vegetable oil, epoxydecane fatty oils, etc.

In addition, preparations containing the compounds of formula (1) according to the invention can be used as a mixture or composition with other agrochemicals, selected on demand from other types of insecticides, acaricides, germicidal, attractants, etc., to achieve a more favorable action.

Insecticides or acaricides, to be used include, for example, organophosphate compounds such as the o - ratioat), the chlorpyrifos-methyl [0,0-dimethyl-0-(3,5,6-trichloro-2-pyridyl)- phosphorothioate] and Arafat (0,S-dimethylaminopropionic); urethane compounds such as carbaryl (1-naphthylethylene), carbofuran (2,3-dihydro-2,2-dimethylbenzofuran-7-yl-methylcarbamate) and methomyl (S-methyl-N-(methylcarbamoyl)-tiazac - aimedat], organochlorine compounds, such as dicofol [2,2,2-trichloro-1,1-bis(4-chlorophenyl)-ethanol]; ORGANOMETALLIC compound, such as fenbutatin oxide [hexacis-(beta,beta-dimethylpentyl)-dis - tannakian]; PYRETHROID compounds such as fenvalerate [(RS)-alpha-cyano-3-phenoxybenzyl-(RS)-2-(4-chlorophenyl)-3 - methylbutyrate)] permethrin [3-phenoxybenzyl ether (1RS)-CIS.TRANS-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylic acid]; compound of benzoylacetone, such as diflubenzuron [1-(4-chlorophenyl)-3-(2,6-differentail)-urea] and chlorfluazuron {1-[3,5-dichloro-4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)-phenyl] -3- (2,6-differentail)-urea], and other compounds, such as buprofezin (2-tert-Butylimino-3-isopropyl-5-phenyl-3,4,5,6-tet - rehydro-2H-1,3,5 - thiadiazin-4-one) and hexythiazox [TRANS-5-(4-chlorophenyl)-N-cyclohexyl-4-methyl-2-oxothiazolidine-3 - carbox - Samid].

Examples of fungicides include organophosphorus compounds, triditional acid); organochlorine connec - tion, such as phtalic (4,5,6,7-tetrachlorophthalic); dithiocarbamate compounds such as polymer zineb [concatemeric-(dithiocarbamate)] and polycarbamate [dicyclic-(dimethyldithiocarbamate)]; -halogenoalkane connections, such as the Cartan [3A, 4,7,7-tetrahydro-N-(trichlormethane - nil) phthalimide] and captafol [3A,4,7,7-tetrahydro-N-(1,1,2,2-tetrachloroethylene)-phthalimide] ; dicarboximide connection such as glycogen [3-(3,5-dichlorophenyl)-N-isopropyl-2,4-dioxoimidazolidin-1-carboxamide] , vinclozolin [(RS)-3(3,5-dichlorophenyl)-5-methyl-5-vinyl-1,3-oxazole - DIN-2,4-DIN] and procymidon [N-(3,5-dichlorophenyl)-1,2-dimethylcyclopropane-1,2-dicar - loximed] ; benzimidazole compounds such as benomyl [methyl ester 1-(butylcarbamoyl)-benzimidazole-2-yl-carbamido acid]; compound of asola, such as bitertanol [1-(diphenyl-4-yloxy)-3,3-dimethyl-1-(1H-1,2,4-triazole-1-yl)- butane-2-ol] and triflumizole {1-[N-(4-chloro-2-triptoreline)-2-propoxymethyl] -imidazole} ; benzanilide compounds such as mepronil (3 isopropoxy-0-toluamide) and flutolanil (alpha, alpha, alpha-Cryptor-3-isopropoxy-0-toluamide).

Representatives of the attractants are benzoic acid, 4-alkyl-2-methoxyphenyl and 4-(para-acetoxyphenyl)-2-b the I powder, granules, dust, dust composition, emulsifying concentrate, flowable liquids, etc. together with the above described auxiliary additives by methods known in obtaining chemicals for agriculture, horticulture or preventing epidemics.

The share of the active compounds of the formula (1) in the range may vary within wide limits depending on the form of the compounds of formula (1), type of drug, etc. Appropriate ratio of compounds should be considered as the interval of 0.01-80 wt.% or more specific depending on the type of drug is 0.01 to 50 wt.%, more preferably 0.1 to 20 wt.% for liquid forms of drugs, such as emulsifying concentrate, wettable powder, flowable composition, etc., or 0.01-20 wt.%, more preferably 0.1 to 10 wt.%, for preparations of solid type, such as a dust, granules, etc.

Preparations containing the compound of formula (1) can be used for combating harmful insects or mites by spraying an effective ingredient of the formula (1) directly on the adults, larvae or testicles insects and/or mites, harmful to agricultural or horticultural cultivated plants, or to prevent epidemics, or in the pockets of finding adults larvae I, depending on the type of active compound, the type of drug, the stage of insects, and so on, the Connection can be applied in a dose of 1-10000 g/ha, preferably 10-1000 g/ha in case of the emulsifying concentrate, liquid preparation and wettable powder they are usually diluted in 1000-10000 times and they can be applied in the amount of 1000-10000 l/ha dust, pulverized composition or granules can be applied in the amount of 10-100 kg/ha.

Below are examples of forms of drugs with compounds of formula (1).

Example of getting the drug 1 (emulgirujushchie concentrate).

Emulgirujushchie concentrate was prepared by adding 80 hours of xylene for 10 hours compound (compound 6 in table.2), 5 p.m alkylarylsulfonate and 5 o'clock alkylsilanes ester polyoxyalkylene.

Example of getting a drug 2 (wettable powder).

Wettable powder was prepared by grinding to a powder mixture of 10 o'clock compounds (compound 145), 5 hours salt Poliak - dialkylanilines ether sulfuric acid, 5 hours salt ligninsulfonate, 10 am, amorphous silica and 70 hours diatomaceous earth.

Example of getting a drug 3 (powdered composition).

Powdered drug was obtained by grinding a mixture of 1 tsp compounds (compound 315), 1 tsp of amorphous silica and 98 is ameriana homogeneous mixture 5 o'clock compound (compound 382), 0.5 hours salt dodecylbenzensulfonate, 3,5 hours salt ligninsulfonate, 30 hours of bentonite and 61 hours of talc with a suitable amount of water, followed by granulation using a granulator, and drying by blowing using a drying apparatus for drying pneumovagina layer.

Example of getting the drug 5 (fluid medium).

Liquid preparation of a homogeneous dispersion of 10 o'clock compounds according to the invention (compound 352), 5 hours alkylsilanes ester polyoxyalkylene, 5 hours of glycol and of 79.5 hours water by stirring followed by the addition of 0.2 tsp xanthan gum as increasing the amount of additives.

The following experimental examples are given to show the excellent activity of the compounds of formula (1) according to the invention as an insecticide or acaricide.

Experimental example 1 (test on the testicles of klasika spider bimaculated).

Each Cup with a diameter of 9 cm was filled with water and covered with a lid with a hole. On the cover was placed a piece of filter paper that has been wetted with water absorption. List of beans were placed on moistened absorbent paper, 10 adult females of clusiifolia eggs for 24 h, then adult females were removed. Drug, obtained by dilution mulgirigala concentrate on the example of getting 1 of water, a predetermined concentration was sprayed on the leaf beans, followed by keeping in the temperature-controlled chamber at 25aboutC for 7 days and oficialno ratio was determined by microscopic examination of the number of hatched larvae. The test was performed 3 times for each area. The results are shown in table.2.

Experimental example 2.

Each Cup with a diameter of 9 cm was filled with water and closed the lid with a hole. On the cover was placed a sheet of filter paper and gave him the opportunity to be wetted by water absorption. On wet filter paper was laid sheet of beans, 10 adult females of klasika spider hanzawa (Tatranychus kanzawai hishida) was inoculable on a sheet of beans and allowed them to postpone the testicles within 24 h, after which adult females were removed. Drug, obtained by dilution mulgirigala concentrate on the example of getting 1 of water with a predetermined concentration was sprayed on the leaf beans, followed by keeping in the temperature-controlled chamber at 25aboutWith t the t was repeated 3 times for each leg. The results are presented in table.2.

Experimental example 3 (acaricide test larvae bimaculated spider Clasica).

Each Cup with a diameter of 9 cm was filled with water and covered with a lid with a hole in it. On the lid was laid sheet of filter paper that has been wetted by water absorption. On moist filter paper was placed a sheet of beans, 10 adult females of klasika bimaculated spider was inoculable on a sheet of beans to lay eggs for 24 h and then removed the adult females. Cups were placed in thermostati - stimulated chamber at 25aboutWith 7 days. Then counted the number of hatched larvae, the drug (obtained in example of preparation 1 dilution with water) mulgirigala concentration - rata predetermined concentration was sprayed on the Cup and kept at 25aboutWith in thermostatic chamber. After 7 LTOs were counted under the microscope the number of surviving adults and received with respect to the number of hatched larvae. The test was repeated 3 times for each area. The results are presented in table.3.

Experimental example 4 (insecticidal test on the nymphs of Myzus persical sulzer).

Every five Beskrovny nymphs for 3 days and then the adults were removed. After this drug, obtained by dilution mulgirigala concentrate on the example of getting 1 of water, a predetermined concentration was applied by spraying on the germination of radish. The treated seedlings were placed in the greenhouse to determine the number of surviving nymphs after 96 h and obtain pesticide. The test was repeated 3 times for each habitat. The results are presented in table.4.

Experimental example 5 (insecticidal test on the nymphs of the aphid cotton).

Every five apterous adult cotton aphid (Aphis gossypii Chovu) was placed on the radish seedling stage in the second sheet, placed in a Cup, let the output of the nymphs for 3 days and then the adults were removed. After this drug, obtained by dilution mulgirigala concentrate on the example of getting 1 of water, a predetermined concentration was sprayed on the seedlings. The treated seedlings were placed in the greenhouse to determine the number of surviving nymphs after 96 h and obtain pesticide relations. The test was performed 3 times for each habitat. The results are presented in table.4.

Experimental example 6 (pesticide test nymphs Hephotettix chicti-ceps).

Every 10 nymphs Hephotettix cinchicepr-cal is the principal drug, obtained by diluting mulgirigala concentrate on the example of getting 1 with water to a predetermined concentration, followed by drying in air and each Cup was covered with a cylinder made of acrylic resin with a gauze net. The treated seedlings were placed in the greenhouse to determine the number of nymphs through 7 Nam and obtain pesticide relations. The tests were repeated 3 times for each habitat. The results are presented in table. 5.

Experimental example 7 (pesticide test on larvae of the cabbage moth).

Every 15 hatched larvae of the cabbage moth (Plutella xylostella Linne) was placed in a Cup with a diameter of 9 cm with leaf cabbage (2 cm2), pre-pogrujennym in the pharmaceutical preparation obtained by dilution mulgirigala concentrate on the example of preparation 1 with water, a predetermined concentration, followed by air drying and determination of pesticide relationship in 4 days. The test was repeated 3 times for each habitat. The results are presented in table.6.

Experimental example 8 (pesticide test on larvae of Culex-pipiens).

Approximately every 15 larvae of the second stage of Culex-pipiens was inoculable in the Cup, with a capacity of 120 ml containing 50 ml of the medicinal product, entrala with the addition of a very small amount of powder of dry yeast as food. The number of larvae of the third stage of development was calculated through 3 days after release and was determined pesticide. The test was repeated 3 times for each area. The results are presented in table.7.

DERIVATIVES OF 2-SUBSTITUTED PHENYL-2-OXAZOLINE OR 2-SUBSTITUTED PHENYL-2-THIAZOLINE AND INSECTICIDAL AND/OR ACARICIDAL COMPOSITION BASED ON THEM.

1. Derivatives of 2-substituted phenyl-2-oxazoline or 2-substituted phenyl-2-thiazoline General formula

< / BR>
where R1and R2- same or different, hydrogen, halogen, lower alkyl, lower alkoxygroup, the nitro-group, a lower haloalkyl group or lower haloalkoxy provided that R1and R2at the same time do not represent hydrogen;

R3is hydrogen, halogen, lower alkyl or lower alkoxygroup;

R4- C7- C20-alkyl, C7- C20-alkoxygroup, C1- C20-allylthiourea, lower alkoxy lower alkyl group, lower alkoxy lower alkoxygroup, C3- C15-alkenylacyl lowest alkyloxy, tri-(lower alkyl)-silyl group or a C3- C8-cycloalkyl group which may be substituted by lower alkyl gr is Kilinochchi, lowest alkylenedioxy or di(lower alkyl) silyl group;

Q is the group - CH or nitrogen;

n is 0 or an integer from 1 to 5;

R5- halogen, C1- C20is an alkyl group, a C1- C20-alkoxygroup, lower haloalkyl group, lower haloalkoxy or tri-(lower alkyl)silyl group, if n is greater than 1, R5may be the same or different;

A is a direct bond or lower Allenova group;

Z is sulfur or oxygen.

2. Derivatives under item 1, wherein R1and R2- same or different, hydrogen, a halogen, a methyl group, a methoxy group, a nitrogroup, triptorelin group or tripterocarpa provided that R1and R2at the same time cannot be represented by hydrogen.

3. Derivatives under item 1, wherein R1and R2are in the 2-, 4 - or 6 - position in a specified substituted phenyl group.

4. Derivatives under item 1, wherein R1and R2each halogen.

5. Derivatives under item 1, wherein R4located in the 4 - position in a specified substituted phenyl group.

6. Derivatives under item 1, characterized in that th the e l e C oxygen, a methylene group or melanochroa;

Q is the group - CH or nitrogen;

n is 0 or an integer from 1 to 5;

R5- halogen, C1- C20is an alkyl group or a C1- C20-alkoxygroup and if n is greater than 1, R5may be the same or different.

7. Derivatives under item 1, wherein A is a direct link.

8. Derivatives p. 1, wherein Z is oxygen.

9. Derivatives under item 1 , wherein A is a direct bond, R1and R2- same or different, are located in the 2 - and 6 - position in a specified substituted phenyl group and represent halogen, R4located in the 4 - position in a specified substituted phenyl group.

10. Derivatives under item 9, wherein R4- C7- C12is an alkyl group or a group of the General formula

< / BR>
where B is a direct bond, methylene group, melanochroa or oxygen;

R5- halogen, C1- C20is an alkyl group, a C1- C20-alkoxygroup and if n is greater than one, R5may be the same or different;

Q is the group - CH or nitrogen;

n is 0 or an integer from 1 to 5.

11. The Insa is jaś fact, as the active ingredient it contains 0.01 - 80,00 wt.% 2-substituted phenyl-2-oxazoline or 2-substituted phenyl-2-thiazoline General formula

< / BR>
where R1and R2- same or different, hydrogen, halogen, lower alkyl, lower alkoxygroup, the nitro-group, a lower haloalkyl group or lower haloalkoxy provided that R1and R2at the same time do not represent hydrogen;

R3is hydrogen, halogen, lower alkyl or lower alkoxygroup;

R4- C7- C20-alkyl, C7- C20-alkoxy group, a C1- C20-allylthiourea, lower alkoxylate alkyl group, a lower alkoxylate alkoxygroup, C3- C15-alkenylacyl lowest alkyloxy, tri-(lower alkyl)silyl group, a C3- C8-cycloalkyl group which may be substituted by a lower alkyl group, or a group of the General formula

< / BR>
where B is a direct bond, oxygen, lower Allenova group, lower accelerograph lowest alkylenedioxy or di(lower alkyl)silyl group,

Q is the group - CH or nitrogen;

n is 0 or an integer from 1 to 5;

R5- halogen, C1- C20-alcopa or tri-(lower alkyl)silyl group, if n is greater than 1, R5may be the same or different;

A - direct connection or lower Allenova group;

Z is sulfur or oxygen.

 

Same patents:

The invention relates to new biologically active chemical compounds, in particular to cyclic amino compounds of the formula I

BANwhere In - perederina, piperidinyl or pyrrolidinyl group, each of which may be substituted by a lower alkyl group, lower alkylcarboxylic group, carbobenzoxy, afterburner (lower) accelgroup, phenylketone (lower) alkyl group, phenylcarbamoyl (lower) alkyl group or phenyl (lower) alkyl group, each of which may be substituted by a halogen atom or a lower alkoxygroup; p is 1 or 2; And -- is a bond, or two-, or trivalent aliphatic C1-6hydrocarbon residue which may be substituted by a lower alkyl group, oxo, hydroximino or hydroxy-group;means either simple or double bond, provided that when a represents a bond, thenmeans of a simple bond; R2and R3independent means ATO condition, both R2and R3are not hydrogen atoms, or R2and R3together with the adjacent nitrogen atom form piperidino, hexamethyleneimino, morpholino, pyrolidine, pieperazinove or 1-imidazolidinyl group, each of which may be substituted by a lower alkyl group, a phenyl (lower) alkyl group, a lower alkylcarboxylic group or diphenyl (lower) alkyl group or a physiologically acceptable salt additive acid

The invention relates to a series of racemic and optically active derivatives of pyrido[1,2-a] pyrazine, which are used as antidepressants and anxiolytics, as well as intermediates of these derivatives

FIELD: organic chemistry, pesticides, agriculture.

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

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

EFFECT: valuable pesticide properties of compounds.

7 cl, 3 tbl, 14 ex

FIELD: agriculture.

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

EFFECT: seed pickling composition of improved quality.

6 cl, 6 tbl, 5 ex

FIELD: agriculture, organic chemistry.

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

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

4 cl, 15 tbl, 15 ex

FIELD: organic chemistry, insecticides.

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

EFFECT: valuable biological properties of substances.

6 cl, 22 tbl, 6 ex

FIELD: herbicides, agriculture.

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

EFFECT: valuable properties of herbicide agent.

7 cl, 36 tbl, 3 ex

FIELD: chemistry.

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

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

18 cl, 180 ex

FIELD: chemistry.

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

EFFECT: high fungicide activity.

22 cl, 142 tbl, 34 ex

FIELD: agriculture.

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

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

2 cl, 9 tbl, 6 ex

FIELD: agriculture.

SUBSTANCE: substituted pyrazole-carbonic anilide derivatives of formula (I) are described, where R1 represents H, alkyl, alkyl carbonyl, alkenyl carbonyl, phenyl alkyl, phenyl carbonyl; R2 represents H, halogen, alkoxy; G represents alkyl, alkenyl; Z represents O; X represents H, halogen, alkyl; Y1 represents alkyl, alkenyl; Y2 represents halogen, C1-C6alkyl, m is equal to 1 or 2; and n is equal to 1, and their salts, acaricide for agriculture, such as pyrazole carbonic anilide derivatives of formula (I) and method for its application. Intermediate compound of formula (II) is also described, as well as 1.3-dimethyl-5-trifluoromethylpyrazole-4-carbonic acid.

EFFECT: improved use of new acaricides.

12 cl, 5 tbl, 20 ex

FIELD: medicine.

SUBSTANCE: there are described synergistic fungicidal combinations of biologically active substances which contain one carboxamide of general formula (I) , (group 1) where A, R1, R2 and R3 have values presented in the patent claim, and a biologically active substance chosen from compound groups specified in the patent claim (2) - (17) have. There is described application of said agent for undesired plant pathogenic fungi control.

EFFECT: extended range of the agents for undesired plant pathogenic fungi control.

8 cl, 13 tbl, 12 ex

FIELD: biology, medicine.

SUBSTANCE: invention relates to chemical compounds and compositions that can be used as modulating agents of phototoxicity of skin cells. Proposed "modulators" relate to material that can either accelerate or decelerate damage of cells, for example, skin cells caused by effect (exposition) of light, for example, UV-rays of type A. Modulators are chosen from group consisting of 3-hydroxyproline pharmacophor or proline, 4-hydroxyproline or its alkyl ester. Invention provides modulating effect of phototoxicity of cells wherein modulators relate to molecule that can be molecule of skin components, in particular, collagen.

EFFECT: improved and enhanced method of modulation.

14 cl, 2 tbl, 13 dwg, 10 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of converting group >C=O (I) in a compound into group >C=S (II) or into a tautomeric form of group (II) in a reaction resulting in a thionated reaction product when using the crystalline P2S5·2C5H5N as a thionizing reagent, as well as to a thionizing agent, that is a crystalline P2S5·2C5H5N and has the melting point of 167-169 °C.

EFFECT: proposed is a novel method of converting group >C=O (I) in a compound into group >C=S (II).

22 cl, 3 tbl, 4 dwg, 7 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing 3,5-dimethylpyridine. Method involves reaction of propanol-1, formaldehyde and ammonia in presence of granulated binder-free zeolite Y-BS in Η-form at 250–450 °C and volume rate of supply of raw material (w), equal to 2-7 h-1, molar ratio of propanol-1: formaldehyde: ammonia is 1.0:0.2–2.0:1.5–5.

EFFECT: use of present method enables to obtain 3,5-lutidine with high volume rate of supply of raw material with high output.

1 cl, 1 tbl, 1 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a novel compound, specifically a tritium-uniformly labelled (3aS,5S,6R,7aR,7bS,9aS,10R,12aS,12bS)-10-[(2S,3R,4R,5S)-3,4-dihydroxy-5,6-dimethyl-2-heptanyl]-5,6-dihydroxy-7a,9a-dimethylhexadecane hydro-3H-benzo[c]indeno[5,4-e]oxepin-3-one of formula:

,

which can be used in analytical chemistry and biological research.

EFFECT: improved properties of the compound.

1 cl, 1 ex

FIELD: medicine, pharmaceutics.

SUBSTANCE: invention refers to a new compound presented by general formula (I): (wherein R1 represents (1) COOH, (2) COOR2, (3) CH2OH or (4) CONR3R4, R2 represents C1-C6 alkyl group optionally substituted by hydroxy group or C1-4 alkoxy group, each R3 and R4 independently represents hydrogen atom or C1-4 alkyl group optionally substituted by ONO2 group, R5 represents halogen atom, hydroxy group or C1-4 alkoxy group, Z represents (1) -(CH2)m-, (2) -(CH2)n-CH=CH-, (3) -(CH2)p-A-CH2-, (4) phenyl or (5) thiazol, A represents oxygen atom or sulphur atom, W represents C1-6 alkyl group optionally substituted by 1-5 substitutes specified in a group consisting of (1) hydroxy group, (2) oxo group, (3) halogen atom, (4) C1-4 alkyl group, (5) C1-4 alkoxy group, (6) ring 2, (7) -O-ring 2 and (8) -S-ring 2, ring 2 represents phenyl, cyclohexyl or pyridinyl, any of which is optionally substituted by 1-5 substitutes specified in a group consisting of (1) halogen atom, (2) CF3, (3) OCF3, (4) C1-4 alkoxy group, (5) C1-4 alkyl group and (6) hydroxy group, m represents an integer having a value of 1 to 6, n represents an integer having a value of 1 to 4, p represents an integer having a value of 1 to 4, represents a single bond or a double bond, represents α configuration, represents β configuration, and represents α configuration, β configuration or a random mixture thereof, or to its salt or its solvate.

EFFECT: invention refers to using this compound, a based pharmaceutical composition, and to a method for preventing and treating ophthalmic diseases, as possesses the potent and stable action for intraocular pressure reduction, and besides has no side effects on the eyes, such as eye irritation (hyperaemia, corneal opacity, etc), higher protein concentration in the intraocular fluid, and hence possesses higher safety and can be an excellent remedy for preventing and/or treating glaucoma.

11 cl, 13 dwg, 9 tbl, 105 ex

FIELD: organic chemistry, agriculture.

SUBSTANCE: substituted benzoylisoxazols of general formula I are described, wherein R1 is cycloalkyl; R2 is hydrogen, alkoxycarbonyl; R3 is halogen, substituted alkyl, alkoxyl; R4 is halogen, alkoxil; Z is substituted 5-membered saturated or unsaturated heterocycle having 1-3 nitrogen atoms and additionally including one oxogroup (C=O). Also disclosed is herbicidal agents, containing compounds of formula I.

EFFECT: effective suppression of weeds in such cultures as maize and wheat.

16 cl, 6 tbl, 4 ex

FIELD: organic chemistry, chemical technology, medicine, pharmacy.

SUBSTANCE: invention describes derivatives of benzodiazepine of the general formula (I)

and their pharmaceutically acceptable acid-additive salts wherein X means a ordinary bond or ethynediyl group; when X means ordinary bond then R1 means halogen atom, (lower)-alkyl, (lower)-alkylcarbonyl, (lower)-cycloalkyl, benzoyl, phenyl substituted optionally with halogen atom, hydroxyl, (lower)-alkyl, (lower)-alkoxy-group, halogen-(lower)-alkoxy-group or cyano-group; styryl, phenylethyl, naphthyl, diphenyl, benzofuranyl, or 5- or 6-membered heterocyclic ring representing thiophenyl, furanyl, pyridinyl, dihydropyridinyl, tetrahydropyridinyl which are optionally substituted; when X means ethynediyl group then R1 means hydrogen atom, (lower)-alkyl substituted optionally with oxo-group; (lower)-cycloalkyl substituted with hydroxyl; (lower)-cycloalkenyl substituted optionally with oxo-group; (lower)-alkenyl, optionally substituted phenyl; 5- or 6-membered heterocyclic ring representing thiophenyl, thiazolyl, pyridinyl, dihydropyridinyl, tetrahydropyridinyl or dihydropyranyl and substituted optionally; R3 means phenyl, pyridyl, thiophenyl or thiazolyl which are substituted optionally. These compounds can be used for treatment or prophylaxis of acute and/or chronic neurological diseases, such as psychosis, schizophrenia, Alzheimer's disease, disorder of cognitive ability and memory disorder. Also, invention describes a medicinal agent based on these compounds and a method for preparing compounds of the formula (I).

EFFECT: improved method for preparing, valuable medicinal properties of compounds.

10 cl, 1 tbl, 173 ex

FIELD: organic chemistry, medicine, pharmacy.

SUBSTANCE: invention describes derivatives of benzodiazepines of the general formula (I):

wherein X means ordinary bond or ethynediyl group wherein if X mean ordinary bond then R1 means halogen atom or phenyl substituted with halogen atom optionally or (C1-C7)-alkyl group; in case when X means ethynediyl group then R1 mean phenyl substituted with halogen atom optionally; R2 means halogen atom, hydroxy-group, lower alkyl, lower alkoxy-group, hydroxymethyl, hydroxyethyl, lower alkoxy-(ethoxy)n wherein n = 1-4, cyanomethoxy-group, morpholine-4-yl, thiomorpholine-4-yl, 1-oxothiomorpholine-4-yl, 1,1-dioxothiomorpholine-4-yl, 4-oxopiperidine-1-yl, 4-(lower)-alkoxypiperidine-1-yl, 4-hydroxypiperidine-1-yl, 4-hydroxyethoxypiperidine-1-yl, 4-(lower)-alkylpiperazine-1-yl, lower alkoxycarbonyl, 2-di-(lower)-alkylaminoethylsulfanyl, N,N-bis-(lower)-alkylamino-(lower)-alkyl, (lower)-alkoxycarbonyl-(lower)-alkyl, (lower)-alkylcarboxy-(lower)-alkyl, lower alkoxycarbonylmethylsulfanyl, carboxymethylsulfanyl, 1,4-dioxa-8-azaspiro[4,5]dec-8-yl, carboxy-(lower)-alkoxy-group, cyano-(lower)-alkyl, 2-oxo[1,3]dioxolane-4-yl-(lower)-alkoxy-group, 2,2-dimethyltetrahydro[1,3]dioxolo[4,5-c]pyrrole-5-yl, (3R)-hydroxypyrrolidine-1-yl, 3,4-dihydroxypyrrolidine-1-yl, 2-oxooxazolidine-3-yl, carbamoylmethyl, carboxy-(lower)-alkyl, carbamoylmethoxy-, hydroxycarbamoyl-(lower)-alkoxy-, lower alkoxycarbamoyl-(lower)-alkoxy-, (lower)-alkylcarbamoylmethoxy-group; R3 means phenyl, thiophenyl, pyridinyl that are substituted with halogen atom, cyano-group, carbamoyl, imidazolyl, 1,2,3-triazolyl, 1,2,4-triazolyl or isoxazolyl wherein groups of 1,2,3-triazolyl, 1,2,4-triazolyl or isoxazolyl are substituted optionally with (C1-C7)-alkyl or (C1-C7)-alkylsulfanyl, and to their pharmaceutically acceptable salts. Also, invention describes a medicinal agent that is antagonist of mGlu receptors of the group II based on compound of the formula (I). The medicinal agent can be used in treatment and prophylaxis of acute and/or chronic neurological disturbances including psychosis, schizophrenia, Alzheimer's disease, disturbances in cognitive ability and memory damage.

EFFECT: valuable medicinal properties of compounds.

7 cl, 1 tbl, 98 ex

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