Derivatives arylpyrol, the retrieval method, the intermediate and the method of controlling insects, nematodes and mites

 

(57) Abstract:

Use: to control insects, nematodes and mites. Entity: products: derivatives arylpyrol f-ly 1, where X is CL; Br, J or CF3; y is CL, Br, J, CF3or CN; W is CN or NO2; A is hydrogen; C1- C4- alkyl; unsubstituted or substituted with halogen, hydroxy, C1- C4alkoxy, C1- C4alkylthio or phenyl group, phenoxy or C1- C2alkoxyphenyl group; C1- C4- carbalkoxy; C3- C4alkenyl, unsubstituted or substituted with one halogen; cyano; C3- C4- quinil, unsubstituted or substituted with one halogen; di (C1- C4alkylaminocarbonyl, L is hydrogen, fluorine, chlorine or bromine; and M and R each independently represents hydrogen, C1- C3alkyl, C1- C3alkoxy, C1- C3- alkylsulfonyl group, cyano, fluorine, chlorine, bromine, iodine, nitro, CF3group R1CF2Z or R2CO, where Z is oxygen, R1- fluorine, or CHF2, R2- C1- C3- alkyl. Reagent 1: benzoylacetonitrile or nitroacetophenone f-crystals 2, where L, M, R and W as mentioned above. Reagent 2: 2,2 - di (C1- C4alkoxy) ethylamine. 4 S. p. f-crystals. With rolevye connection which is highly effective insecticidal, acaricidal and nematocidal means. In addition, this invention provides for the protection of agricultural crops during the growing and harvesting against the harmful effects of the said pests.

The present invention is also directed towards methods of obtaining arilpirolului connections.

New derivatives of arylpyrol have the General formula:

X_ where X is chlorine, bromine, iodine or CF3;

Y is chlorine, bromine, iodine, CF3or CN;

W is CN or NO2;

And hydrogen; C1-C4-alkyl, unsubstituted or substituted with halogen, hydroxy, C-C4-alkoxy, C1-C4-alkylthio or phenyl group, phenoxy-or1-C2-alkoxyphenyl group; C1-C4-carbalkoxy; C3-C4alkenyl, unsubstituted or substituted with one halogen; cyano; C3-C4-quinil, unsubstituted or substituted with one halogen; di(C1-C4)alkylaminocarbonyl; L is hydrogen, fluorine, chlorine or bromine; and M and R each independently represents hydrogen, C1-C3-alkyl. WITH1-C3alkoxy, C1-C3alkylsulfonyl group is a torus or F2, R2C1-C3-alkyl, and when M and R are in adjacent positions, they, together with the carbon atoms which are linked, form a ring, where the group MR is-CH=CH-CH=CH-.

Additionally, the invention relates to new intermediate compounds for obtaining derivatives arylpyrol derived-nitro-lanosterol, in particular: -(2,2-di(C1-4alkoxy)ethylamino)- -lanosterol and - (2,2-di(C1-4alkoxy)ethylamino)- -nitrostyrene General formula

where L, M, R and W have the above values.

These intermediate compounds are obtained at one stage of the method of obtaining derivatives arylpyrol General formula 1, namely, that benzoylacetonitrile or nitroacetophenone General formula

-CH2W where L, M, R and W have the above meanings, is subjected to the interaction with 2,2-di(C1-4alkoxy)ethylamine and obtained respectively -(2,2-di (C1-C4alkoxy)ethylamino)- -lanosterol or -(2,2-di(C1-C4alkoxy)ethylamino)- -nitrosothiol treated with a mineral or organic acid.

Examples of some benzoylacetonitrile in the following table.1.

In addition, the invention relates to a spot, as arylpyrol used as a compound of General formula 1 (where the value of the radicals listed above) in an effective amount.

Arylpyrazole of the present invention are effective for controlling insects, parasitic mites and nematodes. These compounds are also effective for protecting cultivated or collected as a crop from the attack of these pests.

In practical terms, they are usually effective in the approximate range from 10 to 10000 hours per million, and preferably about 100 to 5000 hours per million arylpyrol formula 1, covering all isomers arylpyrol, dispersed in water or other cheap liquid medium when applied at planting material of cultivated crops or the soil where it is grown mentioned planting material to protect it from the attack of pests.

When applied to the foliage of planting material and/or soil or water, where they grow such material damage to the quantity must be sufficient to provide the amount of the active ingredient in the range from 0.125 to 4.0 kg/ha Obviously possible to use higher otnay nematodes and parasitic mites. However, higher relations of applying it is not usually necessary to avoid waste. Although arylpyrazole according to this invention is effective in itself for pest control, they can be used together with other biologically active chemicals, including other insecticides, nematicides and acaricides.

Convenient to the above-mentioned allberry was part of the recipe. These include dry compact granules, flowable compositions, wettable powders, mulgirigala concentrates, dusty, concentrates Farrukh Dustov, microemulsions, etc., capable of application to soil, water and/or foliage and provide the necessary protection of plants. Such formulations include compounds according to the invention in a mixture with inert, agricultural-acceptable solid or liquid diluents. Liquid formulations of the compounds according to the invention, to be sprayed, should contain about 0.001 to 0.1 wt. active arylpyrol.

In terms of use in row crop use volumes of 200-500 l/ha, which usually corresponds to a dose of 0.02-0.05 kg/ha at the dose of 100 ppm and 0.2-0.5 kg/ha at the dose of 1000 h/million

Similarly, when used in the garden p h/million (see tab. 2).

P R I m e R 1. 2-phenylpyrrole-3-carbonitrile.

Following a procedure similar to the method described in Joh 43, 4273-6(1978). Stir magnetic stirrer, the mixture of 30.00 g of N-formyl-phenylglycine heated at 90aboutWith 1.5 hours Clear yellow reaction solution was concentrated in vacuo, giving 42.5 g of oily brownish-orange semi-solid material. Part of the material is purified chromatographically on silica gel showed according to proton NMR spectrum, the presence of a mixture of 73% 2-phenylpyrrole-3-carbonitrile and 27% of 2-phenyl-cyano-5-methylpyrrole. A single recrystallization from chloroform and twice from 1,2-dichloroethane gave 1,69 not quite white solid, proton NMR which showed the presence of 96% 2-phenyl-pyrrol-3-carbonitrile, so pl. 148-152aboutC.

Microanalysis (M. C. 168,19):

Calculated: 78,55; N 4,79; N 16,66%

Found: C 78,52; N To 4.73; N 16,54.

P R I m m e R 2. 4,5-dichloro-2-phenylpyrrole-3-carbonitrile and 5-chloro-2-phenylpyrrole-3-carbonitrile.

To stir with a magnetic stirrer and cooled with ice water to a solution of 2.00 (11.9 mmole) of 2-phenyl-3-cyanoferrate in 80 ml of methylene chloride added in drops within 5 min 1.90 ml (3,19 g; of 23.6 mmole) of sulfurylchloride with a syringe. t-90 minutes The reaction mixture is filtered under vacuum to remove loose precipitated solid (1.28 g), identified as 5-chloro-2-phenylpyrrole-3-carbonitrile, so pl. 192.5 kg-195aboutC. the Filtrate is diluted with 400 ml ethyl acetate, washed with twice 200 ml of water, dried (sodium sulfate), treated with activated charcoal, filtered and then concentrated in vacuo. Received (after resuspension of the residue in hexane) of 0.60 g (21,3% yield) pink-purple solid. This solid is recrystallized from 5 ml of hot acetone, which gives 0.32 g (9% yield) of 4,5-dichloro-2-phenylpyrrole-3-carbonitrile in the form of a brown-orange solid substance, so pl. 254-255aboutC.

H-NMR (dimethylsulfoxide): 7,73 (doublet, j= 6.6 Hz); 1.97 N, 2 phenyl proton at C-2,6), 7,52 (triplet, j=7,3 Hz, 2,04 N, two phenyl proton at C-3,5), 7, 44 (triplet, j=7,3 Hz, 1,02 N, one phenyl proton at C-5), 7,52 (triplet, j=7,3 Hz, 2,04 N, two phenyl proton at C-3,5)

H-NMR (dimethylsulfoxide): 137,51 (p-2 pyrrole carbon), 129,15 (C-4 phenyl carbon), 129,04 (C-3,5 phenyl carbons), 128,37 (C-1 phenyl carbons). 125,88 (2,6 phenyl carbons), to 114.32 (or C-5 of the pyrrole or nitrile carbon), 114,14 (or C-5 of the pyrrole or nitrile carbon), 110,72 (4 pyrrole carbon), 89,78 (p-3 p the Cl 29,74%

P R I m e R 3. p-chloro - a -((formylmethyl)amino)cinnamic nitrile, Diethylacetal.

Stir magnetic stirrer, the solution 250,00 g (1,39 mole) p-chlorobenzalmalononitrile, 203 ml (185,95 g); 1,39 mole of 2,2-diethoxyaniline and 1300 ml of dry toluene is heated under reflux for 20 hours Water collected in the trap Dean-stark (23,8 ml; 95.2% of theory). Hot muddy dark brown solution with a large amount of undissolved solids filtered through a filtering means in the form of hard-shelled land. After dilution with 200 ml of ethyl acetate, the solution is filtered through a 7 cm x 13.5 cm column of silica gel.

The filtrate was concentrated in vacuo, giving 354,38 g (86,4% crude yield) as a clear dark oil that slowly solidified. This solid is recrystallized from hot cyclohexane, giving 324,26 g (79,1% yield) similar to wax orange solid.

NMR of this product showed the presence of 78% (Z ) and 23% (E) isomeric mixture of p-chloro - a -((formylmethyl)amino) cinnamic nitrile, diethylacetal, so pl. 60-72aboutC.

For another, obtained in a similar manner similar samples were obtained the following analytical data:

H-NMR (chloroform), 7,47 (doublet, j=8,6 Gplot; 1,25 N, one N-H proton), 4,69 (Z) 4,60 (E) (triplet, j= 5,1 Hz, 1,05 N, one methine proton acatalog carbon) 4,07 (E) and of 4.05 (Z) (singlet; 0,83 N, adaminaby proton), 3,71 (E) and 3,68 (Z) (Quartet, j=7,1 Hz; 2,22 N, two methylene protons of one of the two ethoxy groups) 3,56 (Z), 3,53 (E) (Quartet, j=7,1 Hz, 2,22 N two methylene proton at one of the two ethoxy groups); 3,18 (triplet; j= 5,1 Hz; 1,77 N, two methylene protons at alleycatallies group), 1,20 (triplet, j= 7,1 Hz; 4,90 N, six methyl protons of the two ethoxy groups).

C-NMR (chloroform), 161,21 ( d-adaminaby carbon); 136,29 (Z) and 134,60 (E) (or C-1 or C-4 phenyl ring), 129,34 (Z) and 129,89 (E) (or C-or 2,6-3,5 phenyl ring), 128,94 (Z) and 128,63 (E) (or C-or 2,6-3,5 phenyl ring), 121,19 (Z) and 119,50 (E) (nitrile carbon), 99,43 (Z) and 100,63 (E) ( -adaminaby carbon), 61,88 (Z) and 63,25 (E) (methylene carbon ethylamino group; 15,26 (methyl carbon of ethoxy groups).

Microanalysis (MV 294,78): Calculated 61,11; N 6,50; N 3,51; Cl A 12.03% Found 61,25; N. Of 6.25; N 9,34; Cl 12,35%

P R I m e R 4. 2-(p-chlorophenyl)-pyrrole-3-carbonitrile.

To 108 ml triperoxonane acid, stirred at 23aboutTo add 54,00 g (0,183 mole) of solid p-chloro - a -((formylmethyl)amino)cinnamic nitrile-diethylacetal within 45 minutes. Due to the exothermic reactor substance. After 30 m of stirring at room temperature the reaction mixture is filtered under vacuum and collected solid is washed first with triperoxonane acid, then with a mixture of ethyl acetate with hexane, and finally with hexane. The output is equal to 16.83 g (45,4) not quite white solid substance, so pl. 165-166aboutC. The sample prepared similarly, we obtained the following data analysis:

H-NMR (acetone): 11,22 (very broad singlet, 0,99 N, 1 pyrology N-h proton), 7,82 (doublet, j=8,9 Hz; 2,46 n, two aromatic phenyl proton), 7,51 (doublet, j=8,9 Hz, 2,46 Hz, two aromatic phenyl proton), 7,02 (triplet, j=2,6 Hz, 1,01 N, one pyrology proton at C-5), to 6.58 (triplet, j=2.6 G; 0,77 N, one pyrology proton at C-4).

C-NMR (acetone) 137,73 (pyrology C-2). 134,42 (p-chloraniline at C-4), 129,93 (methine carbon at C-2,6 phenyl ring), 128,07 (methine carbon at C-2,6 phenyl ring). 121,21 (pyrrole C-5), 117,93 (nitrile carbon), 113,78 (pyrrole carbon at C-4), 90,86 (pyrrole carbon at C-3).

Microanalysis (MV 02,64): Calculated 65,19; N 3,48; N 13,83; Cl 17,50% Found 64,18; N 3,52; N 13,63; CL 17,74%

The application of the above procedures or replacement of concentrated hydrochloric acid triperoxonane acid gave was shadowseeds the data of IR, NMR and elemental analysis.

P R I m e R 5. 4,5-dichloro-2-(p-chlorophenyl)pyrrole-3-carbonitrile.

To stir mechanically solution equal to 16.83 (81,3 mmole) of 2-(p-chlorophenyl)pyrrole-3-carbonitrile in 450 ml of glacial acetic acid at the 36aboutTo add drops of 14.7 ml (24,70 g, USD 183.0 mmole) Sulfuryl chloride for 18 PM Adding connected with increase of temperature up to 39aboutWith the expense of the weak exothermic reaction. Through additional 16 m, the reaction mixture was filtered in a vacuum. The collected solids washed first with acetic acid, then water. This solid after recrystallization from hot ethyl acetate has so pl. 259-261aboutC.

P R I m e R 6. (4,5-dibromo-2-( - Cryptor-n-tolyl)-pyrrole-3-carbonitrile.

To a stirred mixture of 0.8 g of 2-( -Cryptor-p-tolyl)pyrrole-3-carbonitrile in 70 ml of chloroform is added 2 ml of bromine. From the mixture after stirring over night stands white solid collected by filtration. Thin layer chromatography (1: 1 ethyl acetate-hexane) showed the presence of a single component. So pl. more than 230aboutC.

Analysis: for C12H5Br2F3N2Calculated 36,55; N 1.27mm; N 7,11; Br 40,61% Found 36,40; N 1,08; N 6,99; Br 40,55%

Following the tor-p-tolyl)-pyrrole-3-carbonitrile receive the following connections (see table. 4 and 5).

P R I m e R 7. 3-nitro-2-phenylpyrrole.

Alpha-nitro acetophenone (5.7 g; 0,0345 mol) in 100 ml of toluene is added to 4.6 g (0,0345 mole) of diethylacetal of aminoacetaldehyde. The reagents are transferred into a 250 ml round bottom flask equipped with a trap Dean-stark. The trap is filled 4A molecular sieves and the mixture is heated under reflux for 18 hours Removal of toluene in vacuo gives at 8.36 g -(2,2-diethoxyethane)- -nitrostyrene in the form of a brown oil. To this oil is added 50 ml conc. hydrochloric acid. As the rotation of the bulb in a circular motion, the oil turns into a yellow suspension. After 10 min, the solid is filtered off, giving 2,48 g yellow solid. Recrystallization from ether (ethyl acetate) hexane gives the product in the form of 2 fractions:

2,08, So pl. 190-192about(31%).

Max: (1485 cm-1(NO2), H-NMR (deuterated chloroform/dimethyl sulfoxide) was 6.73 (multiplet, 2H); 7,46 (multiplet, 5H).

P R I m e R 8. 2,3-dichloro-4-nitro-5-phenylpyrrole.

A mixture of 3-nitro-2-phenylpyrrole (1.56 g; 0,0083 mol) with 60 ml of dioxane is cooled in a bath of ice as you add drops of 25.9 g (0,0182 mole) sales of sodium hypochlorite. After 45 m mixing, the mixture is acidified with conc. holdem is to see water, dried over anhydrous magnesium sulfate and concentrated in vacuo, giving of 2.21 g of yellow solid.

Purification by chromatography using silica gel and washing with adsorbent with increasing relations with a mixture of ethyl acetate hexane gives after steaming of 0.77 g of yellow solid (36%), so pl. 190-190,5aboutC;

Analysis for C10H6N2O2Cl2< / BR>
Calculated 46,72; H 2,35; N 10,90%

Found 46,96; N 2,86; N 10,02%

Following the procedures of examples 7 and 8. the above, however, using appropriately substituted-nitroacetophenone and 2,2-di(ES1-C4) alkoxy ) ethylamine get substituted-2,2-di (C1-C4alkoxy) ethylamine)- -nitrostyrene, which are then converted into 3-nitro-2-(substituted) phenylpyrrole by treatment with hydrochloric acid, Hydrobromic acid or CF3COOH. The reaction of the thus obtained substituted phenylpyrrole with sodium hypochlorite in dioxane gives the chloro analogs; whereas the reaction of the substituted phenylpyrrole bromine in chloroform leads to the bromine analogues (see table. 6).

P R I m e R 9. 4,5-dichloro-2-(3,4-dichlorophenyl)-1-methyl-pyrrole-3-carbonitrile.

In a 100 ml flask, 2 g of 4,5-dichloro-2-(3,Koti (piperonyl potassium) are added under stirring, that in a few minutes leads to a transparent solution. Add the syringe 1 equivalent J (methyliodide) and the solution heated under reflux for 4 hours the Solution is then left under stirring overnight at room temperature. The next day, add 50 ml of water and the mixture extracted with 4x50 ml of methylene chloride. Received the combined organic phases, dried over magnesium sulfate and concentrated. Received more solid clear instant (flash) chromatography on silica gel using to remove from the adsorbent is a 50/50 ethyl acetate/hexane. This leads to 1,80 g white solid.

Yield 86% so pl. 154-156aboutC.

By following the above procedure, but replacing phenylpyrrole-3-carbonitrile or 3-nitro-2-(substituted) phenylpyrrole not 4,5-dichloro-2-(3,4-dichlorophenyl) pyrrole-3-carbonitrile receive connections below (see tab. 7).

P R I m e R 10. 1-benzyl-4,5-dibromo-2- ( -Cryptor-p-tolyl) pyrrole-2-carbonitrile.

In a 100 ml flask, 1.5 g of 4,5-dibromo-2 - (three fluorine-p-tolyl) pyrrole-3-carbonitrile mixed with 50 ml of dry tetrahydrofuran, which leads to a clear dark solution. Add 1 equivalent of butoxide potassium under stirring. Through several mtim fridge all night. The next day, thin layer chromatography (50/50 ethyl acetate/hexane) showed the presence of both starting material and product. The reaction mixture is processed as follows: add 50 ml of water and the mixture extracted with 4x50 ml of methylene chloride. The combined organic phases are washed with 4x50 ml of 10% aqueous solution of sodium hydroxide. Organic phase is dried over magnesium sulfate and otparivat. This leads to a brown solid substance, which was crystallized from ethyl acetate with hexane. The output of 0.75 g,7% So pl. 145-147aboutC (decomposition).

P R I m e R 11. 4,5-dichloro-2-(3,4-dichlorophenyl)-1-(ethoxyphenyl)-pyrrol-3-carbonita - Rila.

Sample 4,5-dichloro-2-(3,4-dichlorophenyl)pyrrole-3-carbonitrile (1.0 g; of 0.003 mole) dissolved in 10 ml of dry tetrahydrofuran. To this solution was added tert-piperonyl potassium (0,37 g; 0,0033 mole, followed by ethyl ether chlormethyl (0.312 g; 0,0033 mol). The mixture is stirred for about 1 h at room temperature, then poured into a large volume of water, the planting of the product precipitated. White solid is collected and dried, giving 1.0 g (91%), so pl. 128-130aboutC.

P R I m e R 12. 2-chloro-3-cyano-2-(p-chlorophenyl)pyrrole.

To stir with the magnetic stirrer at 20aboutWith RA mmole; 2.00 equivalent of 5.25 wt.-aqueous bleaching funds within 30 PM After an additional 30 min stirring at room temperature the reaction solution was poured in 2200 ml of water. The resulting mixture was filtered in a vacuum, then there is a small amount of black solid. The filtrate is acidified to rn conc. hydrochloric acid, which gives a brown solid. This solid is filtered off under vacuum and the collected solids washed with water, giving 22,41 g brown solid. This solid is treated with 100 ml of 5% aqueous solution of sodium hydroxide to dissolve the bulk, the remaining small amount of undissolved solid black substance. This black solid is dissolved in 100 ml ethyl acetate, washed each time in 75 ml of 5% aqueous sodium hydroxide solution, water and saturated aqueous sodium chloride. An ethyl acetate layer is dried (magnesium sulfate), treated with activated charcoal, filtered, then evaporated in vacuo on a rotary evaporator, giving 1.10 g 5,3% yield Orangevale brown solid. This solid is recrystallized from a mixture of ethyl acetate with chloroform is. 251-253aboutC.

P R I m e p 13. Getting 5-bromo-2-(3,4-dichlorophenyl)pyrrole-3-carbonitrile.

Sample 2-(3,4-dichlorophenyl)pyrrole-3-carbonitrile (2.0 g; 0,008 mole) dissolved in 100 ml of dioxane with heating to 40-50aboutC. Then the solution is cooled to 30aboutWith and add bromine (1.3 g; 0,008 mol). After 1 h stirring at room temperature the solution was poured into water and the grey solid (2.2 g, 88%), So pl. 233-236aboutWith decomposition.

P R I m e R 14. Getting 5-bromo-4-chloro-2-(3,4-dichlorophenyl)-pyrrole-3-carbonite - La.

A sample of 5-bromo-2-(3,4-dichlorophenyl)pyrrole-3-carbonitrile (0,158 g; 0,005 mol) dissolved in tetrahydrofuran (5 ml). Add an equivalent amount of t-butyl hypochlorite and the solution stirred overnight. The solution was poured into water and collect the precipitate (0,052 g, 30%). So pl. more > 275aboutC.

Similarly it is possible to prepare 2-bromo-3-chloro-5-(3,4-dichlorophenyl)- 4-nitropyrrole on the basis of 2-bromo-5-(3,4-dichlorophenyl)-4-nitropyrrole.

P R I m e R 15. Getting 5-bromo-4-chloro-2-(p-chlorophenyl)pyrrole-3-carbonitrile.

To stir with the magnetic stirrer at 22aboutTo a solution of 0.17 g (0.67 mmole; 1.00 equivalent) of 4-chloro-2-(p-chlorophenyl)pyrrole-3-carbonitrile in 100 ml of chloroform, add a drop of the chemical heat. After 3,25 h stirring at room temperature, transparent red reaction solution is evaporated in vacuo, giving 0.28 g not quite white solid. This solid Usacheva in a mixture of hexane with methylene chloride, giving, after vacuum filtration 0,23 g not quite white fluffy solid. So pl. 262-263aboutWith decomposition.

P R I m e R 16. Getting 5-chloro-4-bromo-2-(p-chlorophenyl)-pyrrole-3-carbonitrile.

To stir with the magnetic stirrer at 45aboutTo a solution of 1.00 g (4,22 mmole; 1.00 equivalent) of 5-chloro-2-(p-chlorophenyl)pyrrole-3-carbonitrile in 300 ml of chloroform added in drops over 30 minutes a solution of 0.40 ml (1.24 g; 7,76 mmole; 1.84 equivalent) of bromine in 25 ml of chloroform. Adding not accompanied by the release of exothermic heat. By the end of the add starts the precipitation of small amounts of solids. After 19,5 h stirring at room temperature the reaction mixture is evaporated in vacuo, giving 1,49 g Orangevale-white solid. This solid Usacheva in a mixture of hexane with methylene chloride, after vacuum filtration gives 1,33 g (100% yield) of a fluffy white solid. So pl. 250-258aboutWith decomposition.

P R is th at the 35aboutWith the solution of 2.40 g (11.8 mmole; 1.00 equivalent) of 2-(p-chlorophenyl) pyrrole-3-carbonitrile and 65 ml of glacial acetic acid add drops through syringe 0.75 ml (1.26 g; 9,35 mmole; 0.79 equivalent) Sulfuryl chloride for Approximately 5 m 5 m by the end of the addition of the reaction solution is precipitated solid. After 45 m stirring at room temperature the reaction mixture was filtered and the collected solid is washed thoroughly with cold acetic acid. Gain of 2.08 g (74% yield on crude product) not quite white solid. This substance is recrystallized from 75 ml of hot acetic acid, which gives 1.63 g (58% yield) of the product 97 wt. degree of purity. So pl. 258,5-261aboutC.

P R I m e R 18. Obtain 2-(3,4-dichlorophenyl)-1-methylpyrrole-3-carbonitrile.

In a 100 ml flask 2.0 g of 2-(3,4-dichlorophenyl) pyrrol-4-carbonitrile dissolved in 50 ml of dry tetrahydrofuran and added dropwise 1 equivalent of t-botellita potassium. Get a slightly turbid solution. Then to the mixture is added by pipette 1 equivalent of methyl iodide. This leads to weak enlightenment painting. To the flask and attach a drying tube and left under stirring at ambient temperature overnight.

The following is s and the solution becomes transparent to deposition from a solution of a solid substance. This solid is filtered off from the solution and compare with the original material by the method of thin-layer chromatography (25% ethyl acetate/hexane). It showed the presence of a new single spot moving with greater speed than the original material. Mentioned, the solid is dried in a vacuum drying Cabinet at 50aboutWith all night. Received 1,31 g of product (62% yield). So pl. 140-142aboutC.

P R I m e R 19. Obtain 4,5-dichloro-2-(3,4-dichlorophenyl)-1-methylpyrrole-3-Carbo - nitrile.

In a 50 ml round bottom flask, 0.5 g of 2-(3,4-dichlorophenyl)-1-methylpyrrole-3-carbonita - Rila mixed with 35 ml of acetic acid. The mixture is slightly heated by a heat emitter "dryer" to dissolve all of pyrrole.

To this clear solution was added 2 equivalent Sulfuryl chloride pipette. The solution is kept under stirring at room temperature for 12 h

After 12 h, the solution was poured into 50 ml of water, which caused the appearance of a white precipitate. It is filtered off and dried in a vacuum drying Cabinet at 50about3 o'clock

The obtained solid substance is identical, according to thin-layer chromatography (25% ethylacetate) and infrared analysis of the product of example 9. The output product is SS="ptx2">

To a stirred mixture of 2.0 g (6.5 mmol) of 4,5-dichloro-2-(3,4-dichlorophenyl) pyrrole 3-carbonitrile and 0.88 g (7.8 mmol) of potassium tert-butylate, heated under reflux in 50 ml of dioxane is added 0,98 g (7.8 mmol) of bromoethanol. The mixture is stirred under reflux for 12 h, cooled, diluted with 50 ml of water and extracted several times with chloroform. The combined chloroform extracts are dried over magnesium sulfate and concentrated in vacuo until there is solid. From this substance composition, after heating and dissolving in ethyl acetate, cooling precipitates most of the source of pyrrole. Concentration of the mother liquor and recrystallization of the residual solid substances of 20% ethyl acetate in hexane gives 0.31 g of a white solid substance, so pl. 143-145aboutC; infrared analysis A.

P R I m e R 21. Obtain 4,5-dichloro-2-(3,4-dichlorophenyl)-pyrrole-1,3-dicarbonyl - Rila.

Potassium t-butyl (617 mg, 55 mmol) is added by portions to a solution of 3-cyano-4,5-dichloro 2-(3,4-dichlorophenyl)pyrrole (1.52 g; 5 mmol) in anhydrous tetrahydrofuran (20 ml). After 30 m add a solution of CYANOGEN-bromide (583 mg, 5.5 mmol) in tetrahydrofuran (1 ml). The reaction mixture was kept at room temp with ethyl acetate. The organic layer is washed with water and saturated sodium chloride solution, then dried under magnesium sulfate. Evaporation and crystallization of the residue from ethyl acetate gives white crystals (1.07 g); so pl. 250,5-252,0aboutC; infrared spectrum (nujol) 2255, 2245 cm-1(SP);

13With NMR (dimethylsulfoxide-d6) 102,7 (N-CN); 113,7 (3-CN); mass spectrum 331,9 (M+1).

P R I m e R 22. Obtain 4,5-dichloro-2-(3,4-dichlorophenyl)-1-(3-iodine-2-PROPYNYL)PIR rol-3-carbonitrile.

To stir the mixture at 1.91 g (5.5 mmol) of 4,5-dichloro-2-(3,4-dichlorophenyl)-1-(2-PROPYNYL)-pyrrol-3-carbonitrile in 500 ml of methanol add 69 ml of 10% aqueous solution of hydroaxe sodium. Then 0,70 g (2.7 mmole) of iodine. The mixture was stirred for 12 h, then acidified and diluted with 200 ml of water. Precipitated precipitated solid is collected and recrystallized from methanol, giving 0.51 g of white crystals, so pl. 115-116aboutC.

P R I m e R 23. Obtain 2-(3,4-dichlorophenyl)-4,5-deadparrot-3-carbonitrile.

N-jodatime (5.7 g; 0,0254 mole) is added slowly to a solution of 2-(3,4-dichlorophenyl)pyrrole-3-carbonitrile (3.0 g; 0,0127 mol) in 100 ml of tetrahydrofuran. The reaction mixture is stirred for several hours at 25aboutWith until thin layer chromatography (silica gel; 100:100:1 e is aderrasi pyrrole and succinic acid imide, the crude solid is dissolved in 500 ml of ether and shaken with I ml of water to remove imide succinic acid. The ether layer is dried over sodium sulfate and evaporated in vacuo, leaving 2.0 g (32,3%) grayish-brown solid with so pl. more than 230about(Leaves purple pair).

P R I m e R 24. Getting 2-phenyl-1-pyrrolin-4-carbonitrile.

A solution of Acrylonitrile (0,65 ml of 0.01 mol) and N-trimethylsilyl) methyl-S-methyl-benzothioate (2.4 g; 0,01 mol) in tetrahydrofuran (100 ml) is cooled to minus 5aboutWith in the bath of acetone with ice. By injecting nitrogen add drops of a solution of tetrabutylammonium fluoride (1.0 ml of 1 n solution in tetrahydrofuran) and tetrahydrofuran (20 ml) for 30 minutes the Solution is stirred for further 30 minus minus 5aboutWith, then gradually warmed to ambient temperature. The stirring is continued for another 18 h, then slowly warmed to ambient temperature. The stirring is continued for another 18 h, then the solvent is removed under reduced pressure. The residue is partitioned between ether and water and the aqueous layer was extracted with fresh ether. The combined organic layer washed with water, then saturated sodium chloride solution. Resista (1.2 g; 70%) of theoretical yield. Spectral characteristics of this substance identical to those described in (J.Org. Chem. 52, 2523 (1987)).

So pl. 95-97aboutC.

P R I m e R 25. Getting 2-phenyl-pyrrol-4-carbonitrile.

By injecting nitrogen 2,3-dichloro-5,6-di-cyano-1,4-benzoquinone (0,23 g; 0.001 mol) and 2-phenyl-1-pyrrolin-4-carbonitrile (0.17 g; 0.001 mol) is dissolved in 1,2-dimethoxyethane (13 ml) before formation of a transparent orange solution. Add pyridine (0,08 ml of 0.01 mol) with a single dose that causes a slight warming (approximately 28aboutC) due to the exothermic heat of reaction and immediate formation of greenish-gray precipitate. The suspension is stirred at room temperature for 18 h, and during this time evaporated the solvent most part. Brown semi-solid residue partitioned between ether and saturated sodium carbonate solution. Red-brown aqueous layer was extracted twice with ether, the combined ether layers are washed with fresh water, then a saturated solution of sodium chloride. After drying over magnesium sulfate the solvent is removed under reduced pressure, which leads to a white semi-solid substance. This material is recrystallized from ethylthiourea N 16,67; Found: 78,65; N 4,70; N 16,43;

So pl. 156-158aboutC.

P R I m e R 26. Obtaining 2,4-dibromo-5-phenyl-pyrrol-3-carbonitrile.

By injecting nitrogen a solution of bromine (0.6 ml; 0,012 mol in chloroform (5 ml) is added in drops within 20 m to stir a solution of 2-phenyl-pyrrol-4-carbonitrile (0.84 g; 0.05 m) in chloroform (20 ml). The resulting solution was stirred 18 h at room temperature, the solvent is removed under reduced pressure, giving a solid which is recrystallized from ethylene dichloride (AND WITH). Get the desired target product (0.6 g), so pl. 239-242aboutC.

By the method described in examples 24, 25 and 26, also receive 2,4-dibromo-5-(p-chlorophenyl)pyrrole-3-carbonitrile. so pl. 270-272aboutC (decomposition).

P R I m e R 27. 3' 4' -dichloro-3-(1,3-dioxolane-2-yl)-propiophenone.

To intensively mix the mixture of shavings of magnesium metal (0.64 g, 26 mmol) in 10 ml of tetrahydrofuran at 25aboutWith 100 ml three-neck round bottom flask equipped with a thermometer, 60 ml of the feeding funnel and a tube for supplying nitrogen add drops of 2-(2-bromacil)-1,3-dioxolan (4.7 g, 26 mmol) in 40 ml of tetrahydrofuran. The speed of adding selected so that the temperature was below the 50including potassium (5.0 g, 22 mmole) under a layer of nitrogen. Then the solution of the Grignard quickly removed by decantation with unreacted magnesium shavings and add drops to the rapidly stirred suspension of potassium benzoate. Then the reaction mixture is stirred for 24 h at 25aboutC. To the reaction mixture are added 50 ml of diethyl ether and 15 ml of 3-n hydrochloric acid and separated layers. The organic layer was washed with saturated aqueous sodium bicarbonate to neutral environment, and then washed once with 10 ml of brine. Drying over magnesium sulfate and evaporation in a rotary evaporator lead to a semi-solid substance, which chromatographic on silica gel using 3:1 hexadecyl acetate to remove from the adsorbent, which gives the keto-acetal (4.3 g; 60%) as a white solid, so pl. 115-117aboutC.

P R I m e R 28. Obtaining 3-(3,4-dichlorobenzoyl)Propionaldehyde.

10 g (26 mmol) of 3' 4' -dichloro-3-(1,3-dioxolane-2-yl)-propiophenone added to 30 ml of 0.2 m oxalic acid (obtained by dissolving 0.9 g of oxalic acid dihydrate in 30 ml of water and 5 ml ethanol. The mixture is heated under reflux for 1 h, then allowed to cool. Most ethanol is evaporated in a rotary evaporator; add 100 ml dietert over magnesium sulfate. Evaporation in a rotary evaporator leads to a yellow viscous oil, which when chromatographicaliy over silica gel using 3:1 hexane-ethyl acetate gave käthe-aldehyde (6.3 g; 75%) as a white solid.

P R I m e R 29. Obtain 2-(3,4-dichlorophenyl)pyrrole.

To a suspension of 3-(3,4-dichlorobenzoyl)Propionaldehyde (6 g, 26 mmole) in 60 ml of absolute ethanol is added ammonium acetate (4 g, 52 mmole). The reaction mixture is refluxed for 20 m and allow to cool. A large part of the ethanol is evaporated in a rotary evaporator and add 200 ml of 1:1 dichloromethane diethyl ether, and then 50 ml of water. The layers are separated and the organic phase is dried over sodium sulfate. Rotary evaporation yields a dark brown oil, which when chromatographicaliy over silica gel and the application to remove from the adsorbent 3:1 hexane-ethyl acetate shows: pyrrole (4.6 g, 83%) as a pale brown solid, so pl. 49-51aboutC.

P R I m e R 30. Getting 5-(3,4-dichlorophenyl)pyrrol-2-carboxaldehyde.

To 10 ml of dimethylformamide, stirred under a layer of nitrogen in a 50 ml round bottom flask was added phosphorus oxychloride (0.6 ml; 6.5 mmol) drops by means of a syringe. The solution stanovitsya portions.

The resulting beige suspension is stirred for 30 m, then heated to 50aboutWith 40 meters To the cooled reaction mixture is added a solution of sodium acetate (10 g, 122 mmole) in 15 ml of water. The mixture is stirred for 20 m Beige precipitate was filtered from the reaction mixture and dried in air for 20 h, which gives essentially pure aldehyde (1.1 g, 95%), so pl. above 200aboutC.

P R I m e R 31. Getting 5-(3,4-dichlorophenyl)pyrrol-2-carbonitrile.

To a suspension of 5-(3,4-dichlorophenyl) pyrrol-2-carboxaldehyde (1.5 g, 6.2 mmole) in 20 ml of water and 20 ml of ethanol is added hydroxylamine-0-acid (0.7 g; 6.2 mmole). The reaction mixture is refluxed 1 h During this time, a grey precipitate. After cooling, the reaction mixture is filtered, giving essentially pure nitrile (1.5 g, 99%) as a gray solid, so pl. 170-171aboutC.

P R I m e R 32. Obtaining 3,4-dibromo-5-(3,4-dichlorophenyl)pyrrol-2-carbonitrile.

To a solution of 5-(3,4-dichlorophenyl)pyrrol-2-carbonitrile (0.5 g, 2.1 mmole) in 20 ml of tetrahydrofuran under a layer of nitrogen add portions of N-bromo-succinic acid imide (0.8 g; 4.2 mmole). The reaction mixture was stirred at 25about30 m, then add 10 ml of water and 40 ml of diethyl ether. The layers are separated and the eat over silicagel with application to remove from the adsorbent 3:1 hexane ethyl acetate leads to depomedrol (0.5 g, 60%) as a brown solid substance, so pl. 250aboutC.

P R I m e R 33. Getting 4-phenyl pyrrole-3-carbonitrile.

To a mixture of 5.0 g (39 mole) of the nitrile of succinic acid and 7.6 g (39 mmol) (n-tamilselvan) methyl isocyanide in 35 ml of dimethyl sulfoxide and 65 ml of ether is added over a 20 m suspension of sodium hydride (1,11 g, 46 mmol) in 80 ml of ether. The reaction mixture was kept under nitrogen for 1 h, then diluted with ether and water. The ether layer is separated, dried over magnesium sulfate and concentrated in vacuo. The oil obtained chromatographic on silica gel using 1: 1 chloroform: ethyl acetate, giving 2.5 g of solids cream color. Recrystallization from ether-hexane gives to 1.15 g of substance, so pl. 123-125aboutC.

Tetrahedron Letters 5337 (1972), pl. 128-129aboutC.

P R I m e R 34. Obtaining 2,5-dichloro-4-phenylpyrrole-3-carbonitrile.

To stir a mixture of 0.66 g (3.9 mmole) of 4-phenyl pyrrole-3-carbonitrile in 20 ml of dry tetrahydrofuran, cooled to 6aboutWith in the tub with ice added from a syringe to 0.66 ml (1,11 g, 8.2 mmole) Sulfuryl chloride 4 M. the Mixture was kept at 5-10aboutWith the addition of 45 m, and then stirred for further 30 m at a remote ice bath. The reaction mixture is poured into 80 ml of ethyl is through a short column, rinsing with ethyl acetate and concentration of the combined filtrates in vacuo gives 0,95 dark matter. Recrystallization from chloroform gives 0,42 g not quite white crystals, so pl. 195-196about(And decomposition).

Following the procedure of examples 33 and 34 receive the following analogs. For the synthesis of 2,6-dibromo-4-(p-chlorophenyl)pyrrole-3-Carbo - nitrile follows the procedure of example 33, using bromine in dioxane to replace chloride Sulfuryl and tetrahydrofuran (see tab. 8).

P R I m e R 35. Ethyl-4-(p-chlorophenyl)pyrrole-3-carboxylate.

To the mixture 5,63 g of 60% suspension of sodium hydride in oil in 200 ml of dry ether under nitrogen is added from the adding funnel a mixture of 23.5 g (122 mmole) p-chlorocinnamate and of 19.4 g (122 mmole) (p-tamilselvan) methyl isocyanide in solution in 180 ml of ether and 80 ml of dimethyl-sulphide. Duration add about 20 m leads to weak action of the reverse refrigerator the mixture. After an additional 10 m of the mixing, the mixture is diluted with 100 ml of water. The mixture is extracted 4 times with ether, then dried over magnesium sulfate, followed by concentration in vacuo. The obtained solid is recrystallized from ethylene dichloride, which gives 7,8 g of crystals, so pl. 137-138aboutenyl)pyrrole-3-carboxylate after recrystallization mother liquor and recrystallized product after the previous step was stirred at step backward refrigerator with 150 ml of 10% aqueous sodium hydroxide solution of 2.5 hours The mixture is cooled, extracted with ether and acidified with that gives a precipitate, which, after collecting and drying weighs 11,6,

A mixture of 10.5 g of the acid in 100 ml of ethanolamine heated under reflux for 3 hours After cooling, the mixture was poured onto 400 ml of ice and the resulting mixture is extracted 4 times with chloroform. A chloroform solution after drying over magnesium sulfate and processing of activated carbon was concentrated in vacuo, the resulting brown solid substance. The chromatography was carried out on silica gel using 1:1 ethyl acetate-hexane gives 4.0 g of a white solid substance, so pl. 117-118aboutC.

P R I m e R 37. Obtaining 3-(p-chlorophenyl)-pyrrole-2-carboxaldehyde.

To the mixture 0,86 g (12 mmol) of dimethylformamide in 10 ml of dichloromethane, maintained under nitrogen and cooled in a bath with ice, add 1,49 g (12 mmol) of oxalicacid in 10 ml of dichloroethane at 25 feet, the ice Bath is removed, the mixture is stirred for additional 15 m and re-cooled in an ice bath. To this mixture is added 1.5 g (8.5 mmol) of 3-(p-chlorophenyl)-pyrrole in 25 ml of dichloroethane at 20 feet, the ice Bath is removed and after an additional 30 m of stirring, the mixture was poured into 50 ml ice water with 6 ml of 50% sodium hydroxide. The resulting mixture extras is in vacuum. Purification of the obtained solid by chromatography on silica gel using 1: 1 ethyl acetate hexane, gives 0,63 g not quite white solid. Directly used for transformation to 3-(p-chlorophenyl)-pyrrole-2-carbonitrile.

P R I m e R 38. Obtaining 3-(p-chlorophenyl)-pyrrole-2-carbonitrile.

The mixture was 0.63 g (3.1 mmole) of 3-(p-chlorophenyl)-pyrrole-2-carboxaldehyde in 10 ml of water is stirred and cooled with ice gradually added 0.52 g (4.6 mmole) gidroksilamin-0-sulfonic acids in 10 ml of water. After the addition the ice bath removed and the mixture is heated 25 m

Collected after cooling the resulting solid substance, according to NMR, is a mixture of product and starting aldehyde. This mixture is subjected to reaction in the same manner with an additional quantity of 0.49 (4.2 mmole) of hydroxyl amine-0-sulfonic acids in a total volume of 30 ml of water. The mixture is cooled, the obtained solid is collected and purified by chromatography on silica gel using 1:1 ethylacetate that leads to and 0.46 g of a pink solid, so pl. 114-115aboutC.

P R I m e R 39. Obtaining 4,5-dibromo-3-(p-chlorophenyl)-pyrrole-2-carbonitrile.

To a mixture of 0.40 g (2.0 mmole) of 3-(p-chlorfenapyr)-2-carbonitrile in 25 ml of helotiaceae, that give 0.21 g of pink crystals, so more than 250 squareaboutC.

Analysis for C11H5Br2ClCN Calculated 36,62; N 1,39; Br 44,38; Cl 9,85; N To 7.77; Found 36,92; N 1,32; Br 44,62; Cl 9,88; N 7,50.

P R I m e R 40. Obtain ethyl 5-bromo-4-(p-chlorophenyl)pyrrole-3-carboxylate.

Ethyl 4-(p-chlorophenyl) Pirro-3-carboxylate (1.6 g; 0,0064 mole) is dissolved in tetrahydrofurane (40 ml). Bromine succinic acid (1,14 g; 0,0064 mole) is added in small portions at 25-28aboutC. Upon completion of addition the solution is stirred overnight at room temperature. The solution was concentrated in vacuo and the solid residue partitioned between water and ether. The ether layer is separated and dried over magnesium sulfate. Treatment of the ether extract gives 1.9 g (90% ) of white solid, which is purified by stirring with a mixture of 80/20 hexane with ethyl acetate. Undissolved solid (1.3 g; 62%) gather. So pl. 161-164aboutC.

P R I m e R 41. Getting 5-bromo-4-(p-chlorophenyl)pyrrole-3-carboxylic acid.

Ethyl 5-bromo-4-(p-chlorophenyl)pyrrole-3-carboxylate 15 g; 0,045 mol) are added to 200 ml of 10% hydroaxe sodium and the suspension is heated under reflux. After all dissolved, the mixture is cooled, filtered, and the filtrate is acidified. Belalugosi), showing pyrology proton at 7,52 (doublet). The mass spectrum also coincided with those for monobromobimane connection.

P R I m e R 42. Obtain 2-bromo-3-(p-chlorophenyl)pyrrole.

5-bromo-4-(p-chlorophenyl) pyrrole-3-carboxylic acid (8.0 g; 0,026 mol) are added to aminoethanol (24 ml) and the suspension is slowly heated to 110-120aboutC and kept at this temperature for 1 h the Solution is cooled, poured into water and extracted with ether. The ether extract according to thin-layer chromatography (75/25, hexane/ethyl acetate) showed the main fast-moving spot and slower moving secondary component. Treatment of the ether left a dark solid (4.0 g, 56%), representing 2-bromo-3-(p-chlorophenyl)pyrrole, which is directly used for the preparation of 5-bromo-4-(p-chlorophenyl)pyrrol-2-carbonitrile.

P R I m e R 43. Getting 5-bromo-4-(p-chlorophenyl)pyrrol-2-carbonitrile.

A freshly prepared sample of 2-bromo-3-(p-chlorophenyl)pyrrole (4.0 g; 0,015 mol) dissolved in dry dimethoxyethane (25 ml). Then, while maintaining the temperature below 25aboutTo add chlorosulfonyl isocyanate is 3.08 g; 0,022 mol). After stirring overnight the solution is treated with dimethylformamide (6 ml) and stirred for 3 hours Saravia (80/20 hexane/ethyl acetate) gives 1.4 g (33%) of white solids, so pl. 202-204aboutC.

Analysis for C11H6BrClN2Calculated With 46,90; N 2,13; N 9,95;Cl 28.39; Br 12,61; Found, 47,20; H 2,09; N 9,80; CL 12,36; Br 27,42.

P R I m e R 44. Getting 3,5 dibromo-4-(p-chlorophenyl)pyrrol-2-carbonitrile.

A sample of 5-bromo-4-(p-chlorophenyl)pyrrol-2-carbonitrile (2.2 g; 0,0078 mole) is dissolved in 30 ml of dry dioxane. The solution is heated with bromine (1.3 g; 0,008 mol) in dioxane (20 ml), then stirred overnight at room temperature. The reaction mixture was poured into water, followed by precipitation reddish-brown solid (2,6; 92%). A portion (1.6 g) clear instant chromatography using 75/25 hexane/ethyl acetate, giving 0.8 g of gray solid with so pl. 191-194aboutC.

P R I m e R 45. Obtaining 3-(3,4-dichlorophenyl)-4-nitropyrrole.

Sodium hydride (2,66 60% oil suspension, washed with dry ether; 66 mmol) is suspended in 150 ml of dry ether. To this mixture is added over 15 min a mixture of 12.0 g (:6: 5.5 mmol) of 3,4-dichloro - nitrostyrene; 10.8 g (5.5 mmol) (n-tamilselvan) methyl isocyanide in 50 ml of dimethyl sulfoxide and 150 ml of ether. The mixture is stirred for 1.5 h, diluted with 150-200 ml of water and optionally ether. The ether layer is separated, dried over magnesium sulfate and Continium 4:1 mixture of chloroform with ethyl acetate. 7.2 g of fraction solid is recrystallized from chloroform - ethyl acetate-hexane, giving 3.0 g of a yellow solid substance, so pl. 187-188aboutWith e (decomposition).

P R I m e R 46. Obtaining 2,5-dichloro-3-(3,4-dichlorophenyl)-4-nitropyrrole.

To a mixture of 3-(3,4-dichlorophenyl)-4-nitropyrrole (2.5 g, 9.7 mmol) in 200 ml of chloroform is heated to approximately 40aboutWith add for 1 min 2,95 g (22 mmole) Sulfuryl chloride. After 1 h the mixture is diluted with 100 ml saturated sodium bicarbonate solution and 300 ml of ether. The organic layer is separated and dried over magnesium sulfate. After concentration in vacuum remains brown solid, which chromatographic on silica gel using 4: 1 chloroform-ethyl acetate. Faction orange solid is recrystallized from chloroform, then chromatographic on silica gel using 4: 1 chloroformmethanol that give 0.36 g of a yellow solid substance, so pl. 193-194aboutC.

Also prepared by the above procedures of examples 45 and 46 2,5-dichloro-2-nitro-4-phenylpyrrole, so pl. 193-194aboutC (decomposition).

P R I m e R 47. Getting 5-(p-chlorophenyl)pyrrole-2,4-dicarbonitrile.

Sample 2-p-chlorophenyl-3-cyanoferrate, photofinisher isocyanate (3,39 g; 0,024 mol). The addition is accompanied by an exothermic reaction that requires some cooling. After 3 h stirring at room temperature, add dimethylformamide (6-7 ml) and the solution stirred for further 4 h the Solution was poured into water. Precipitated white solid (3.4 g, 100%). A sample (1.0 g) is purified by dissolution in ethyl acetate and the transmittance of the solution in 60 ml filter funnel filled with silica gel. The filtrate is concentrated, giving 0.7 g of a white solid substance, so pl. 235-240aboutC.

Following the procedure of example 47, obtain the following analogues (see table. 9).

P R I m e R 48. Obtain 2-bromo-5-(p-chlorophenyl)pyrrole-3,4-dicarbonitrile.

Sample 5-(p-chlorophenyl)pyrrole-2,4-dicarbonitrile (1.0 g, of 0.004 mole) was dissolved in 20 ml of dioxane and the solution is added a solution of bromine (0.8 g; 0,005 mol in dioxane (10 ml). The solution is stirred for several hours at room temperature, then poured into water, followed by precipitation of a white solid (1.2 g, 100%). The solid is so square over 225aboutC. Mass spectrum of the sample has lattice matching with the desired structure.

Following the procedure outlined in example 48, will receive the following additionally the Otomi, fumaronitrile (15,6 g; 0.2 mol in chloroform (150 ml) is heated under reflux, resulting in a transparent solution. A solution of bromine (5,3 mole; 0,2 mol) in chloroform (25 ml) is added in drops over 30 minutes This leads to a gradual discoloration, and are allocated acid (pH indicator paper). The solution is heated under reflux for 90 m During this time a large part of the painting disappears. The solution is cooled and the solvent is removed under reduced pressure. Is oil amber color (weight about theoretical for bromomalonate).

The oil is subjected to distillation (0.2 mm RT.CT.) "drop by drop". The temperature of the support below the 120about(Above this temperature there is a rapid decomposition). Receive semi-solid substance that becomes waxy solid amber color, so pl. 43-47aboutC.

P R I m e R 50. Getting 2-phenyl-pyrrole-3,4-dicarbonitrile.

By injecting nitrogen solution bromomalonate (4.7 g; 0,03 mole) and N-(trimethylsilyl)methyl-S-methyl-benzene-timedata (7,1, of 0.03 mol) in hexamethylphosphoramide (HMPA) was stirred at room temperature. Add single serving of water (1.6 ml; and 0.09 mol), washed, HMPA (10 ml). The solution patride than decrease. The resulting dark red solution continued to stir at ambient temperature for 20 hours pour the reaction mixture into a mixture of ice and water, this leads to a resinous material, which gradually passes into a state of disconnected parts solid beige color. This material is collected by filtration and washed with cold water and dried

Sample 5-(p-chlorophenyl)pyrrole-2,4-dicarbonitrile (1.0 g, of 0.004 mole) was dissolved in 20 ml of dioxane and the solution is added a solution of bromine (0.8 g; 0,005 mol in dioxane (10 ml). The solution is stirred for several hours at room temperature, then poured into water, followed by precipitation of a white solid (1.2 g, 100%). The solid is so square over 225aboutC. Mass spectrum of the sample has lattice matching with the desired structure.

Following the procedure outlined in example 48, will receive the following additional connections (see tab. 10).

P R I m e R 49. Getting bromomalonate.

By injecting nitrogen, fumaronitrile (15,6 g; 0.2 mol in chloroform (150 ml) is heated under reflux, resulting in a transparent solution. A solution of bromine (5,3 mole; 0,2 mol) in chloroform (25 ml) is added in drops over 30 minutes This is Renaut under reflux for another 90 m During this time a large part of the painting disappears. The solution is cooled and the solvent is removed under reduced pressure. Is oil amber color (weight about theoretical for bromomalonate).

The oil is subjected to distillation (0.2 mm RT.CT.) "drop by drop". The temperature of the support below the 120about(Above this temperature there is a rapid decomposition). Receive semi-solid substance that becomes waxy solid amber color, so pl. 43-47aboutC.

P R I m e R 50. Getting 2-phenyl-pyrrole-3,4-dicarbonitrile.

By injecting nitrogen solution bromomalonate (4.7 g; 0,03 mole) and N-(trimethylsilyl)methyl-S-methyl-benzene-timedata (7,1 g; 0,03 mole) in hexamethylphosphoramide (HMPA) was stirred at room temperature. Add single serving of water (1.6 ml; and 0.09 mol), washed, HMPA (10 ml). The solution almost immediately heated by the heat of an exothermic reaction. The temperature quickly reaches 100aboutTo before drop. The resulting dark red solution continued to stir at ambient temperature for 20 hours Pour the reaction mixture into a mixture of ice and water, this leads to a resinous material, which is the gradual transition is washed with cold water and dried on the filter. After further drying (vacuum drying oven at 60aboutSince the material is twice recrystallized from dichloroethane (DARCO), which leads to a white powder.

Analysis for C12H7N3< / BR>
Calculated 74,61; N 3,63; N 21,76;

Found 74,45; N. Of 3.84; N 21,61.

So pl. 197-200aboutC.

P R I m e R 51. Obtain 2-bromo-5-phenylpyrrole-3,4-dicarbonitrile.

By injecting nitrogen 2-phenyl-pyrrole-3,4-dicarbonitrile (1.4 g; 0,0075 mole) is added to the chloroform (35 ml), the solvent most part solid. A solution of bromine (0.4 ml; 0,008 mole) in chloroform (5 ml) is added in drops within 20 minutes of Initial staining disappears quickly, however, as starting deposition of the new resinous solids, staining remains. After 30 m of stirring at room temperature the mixture begins to heat under reflux that leads to the formation of solids, consisting of much more discrete fragments. After 90 m of heating under reflux, the reaction mixture is cooled and some largest part removed and analyzed by liquid chromatography, carried out under high pressure (LC). It is shown that the reflux continued additional 45 m, then in particular largest part was in the presence of 10% of the source material. To heated under reflux suspension add another fresh portion of bromine (0.2 ml; 0,004 mol) and heating under reflux continued an additional 30 m, the Suspension is cooled and stirred for 18 h at room temperature. The solvent is removed under reduced pressure, which gives a greenish solid, which was extracted with hot chloroform. In the end remains dark matter. The extract is treated according to the method of DARCO and filtered hot. Clear yellow filtrate quickly starts to produce a white precipitate. After cooling to minus 10aboutC, white solid is collected by filtration.

Analysis for C12H6BrN3Calculated With 52,94; N 2,21; N 15,44; Br 29,41; Found, To 51.64; H 2,35; N 14,91; Br 28,69.

So pl. 225-258aboutC.

P R I m e R 52. Getting 2(3,4-dichlorophenol)-5-nitropyrrole-3-carbonitrile.

2-(3,4-dichlorophenyl)pyrrole-3-carbonita - RIL (3.0 g; 0,013 mol) is added to acetic anhydride (50 ml) and 90% nitric acid (0.6 ml), and is very slight exothermic heat. The mixture is slowly heated to 30aboutC, and then maintained at 30-33aboutat room temperature, then pour in the water and on the ice to decompose acetic anhydride. After 1 h of stirring the mixture is filtered, the collected solid (2.9 g, 82%) and dried. A portion (1.5 g) purified column chromatography on silica gel using 75/25 hexane and ethyl acetate to remove from the adsorbent, giving 0.7 g of yellow solids with so pl. 228-231aboutC.

Analysis for C11H5Cl2N3O2: Calculated 46,80; H 1,77; N 14,89; Cl 25,17; Found 46,50; N 1,96; N 14,27; Cl 24,30.

According to this same methodology, based on 2-(p-chlorophenyl)pyrrole-3-carbonitrile get 2-(p-chlorophenyl)-5-nitropyrrole-3-carbonitril, so pl. 201-206aboutC, 2-(p-triptoreline)pyrrole-3-carbonitrile gives 2-(p-trifluoromethyl phenyl)-5-nitropyrrole-3-carbonitrile, using the above procedure. This connection is so pl. 164-165,5aboutC.

P R I m e R 53. Getting 4-bromo-2-(3,4-dichlorophenyl)-5-nitro-pyrrole-3-carbonita - Rila.

2-(3,4-dichlorophenyl)-5-nitropyrrole-3-carbonitrile (0.5 g; 0,0017 mole) is dissolved in dry dioxane (10 ml). To this solution was added bromine (0.28 g; 0,0017 mol) in dioxane. After stirring overnight the solution was poured into water, followed by precipitation reddish-brown solid (0.54 g, 88%). Perekrest">

Analysis for C11H4BrClN3O2:Calculated 36,57; N 1,10; N 11,63; Br 22,13; Cl 19,67; Found 36,46; H 1,29; N 11,50; Br 21,63; Cl 19,28.

Following the above procedure of example 53, but in terms of 2-(p-chlorophenyl)-5-nitropyrrole-3-carbonitrile, receive a 4-bromo-2-(p-chlorophenyl)-5-nitro-pyrrole-3-carbonitrile, so pl. 180-185aboutC.

P R I m e R 54. 5-(3,4-dichlorophenyl)-4-nitropyrrole-2-carbonitrile.

To a suspension of 5-(3,4-dichlorophenyl)pyrrol-2-carbonitrile (1.2 g; 5.1 mmole) in 25 ml of acetic anhydride at 30aboutTo add drops under a layer of nitrogen 90% nitric acid (0.3 ml; 5.1 mmole). The reaction mixture is heated due to the exothermic reaction up to 45aboutWith and becomes a green solution. After 2 h stirring, the reaction mixture was poured into 50 ml of water, and intensively stirred for 5 m Received a beige precipitate is filtered and dissolved in a minimum quantity of acetone. The chromatography was carried out over silica gel using 3:1 hexane with ethyl acetate gives nitropyrrole (1.2 g; 84%) as not quite white solid substance, so more than 200 squareaboutC.

P R I m e R 55. 3-bromo-5-(3,4-dichlorophenyl)-4-nitropyrrole-2-carbonitrile.

To a suspension of 5-(3,4-dichlorophenyl)-4-nitropyrrole-2-carbonitrile (0.6 g; 2.1 mmol) in 10 minnow the mixture is stirred overnight. Add 50 ml causes the precipitation of a yellow solid, which is collected and dried in a vacuum oven (50 mm RT.article 45about(C) that gives the commercially available brominated pyrrole (0.7 g; 90%) as a yellowish solid substance, so pl. over 200aboutC.

P R I m e R 56. 4-(p-chlorophenyl)-2-(trifluoromethyl)-2-oxazoline-5-he.

Triperoxonane anhydride (1.7 ml; 0,012 mol) add a single portion to powdery 2-(p-chlorophenyl)glycine (11.4 g; 0,06 mol), which causes an immediate warming up to approximately 40aboutDuring the exothermic reaction, and on the surface of a solid substance appears yellow staining. Gradually heating the mixture to 70aboutWith a large part of the solids dissolved to oil orange-amber color. All the solid is dissolved for 2 hours Heating continued for another 1 h the Solvent is removed under reduced pressure in a rotary evaporator. Double-add toluene and remove it under reduced pressure, but the smell triperoxonane acid is still obvious. This yellow semi-solid substance (theoretical output); degree of purity greater than 90% according to liquid chromatography, carried out under high pressure (LC) is identi and m e R 57. Obtain 2-(p-chlorophenyl)-5-(trifluoromethyl)pyrrole-3-carbonita - Rila.

4-(p-chlorophenyl)-2-(trifluoromethyl)-2-OK - Sadolin-5-Oh (2.5 g; 0.01 mol) was dissolved in nitromethane (50 ml). To the solution add a single serving of 2-chloroacrylonitrile (8,0 ml of 0.10 mol) and the resulting solution stirred for 18 h under reflux in a nitrogen atmosphere. Cooling the red-brown solution to minus 5aboutWith in a tub of ice with acetone results in the formation of a precipitate, which is collected by filtration and washed with a small amount of cold nitromethane. The obtained reddish-brown solid is recrystallized from hot dichloroethane, which gives the product as white crystals (1.8 g, 56% of theory), so pl. 238-241aboutC (decomposition).

Through the use of appropriate arigliano when the procedure of example 55, following the procedure of this example, prepare the following 2-aryl-5-(trifluoromethyl)pyrrole-carbonitrile (see tab. 11).

P R I m e R 58. Getting 4-bromo-2-(p-chlorophenyl)-5-(Cryptor)4-methyl)pyrrole-3 - carbonitrile.

By injecting nitrogen, a suspension of 2-(p-chlorophenyl)-5-(trifluoromethyl)pyrrole-5 - carbonitrile (1.6 g, of 0.005 mol) in acetic acid (25 ml) is heated at 60aboutWith until all material is dissolved with obrazovaniia, heated under reflux. The solution is heated so 6 h, then stirred for 18 h at room temperature liquid chromatography was carried out conducted at an elevated pressure of the reaction mixture showed about 80% conversion to the product. The mixture is again heated to reflux and add drops of more bromine (0.5 ml of 0.01 mol) in acetic acid. After further heating under reflux (3 h) selected a certain number showed 95% conversion to product. The reaction mixture is cooled, the solvent is removed under reduced pressure in a rotary evaporator, giving a dark grey solid. To the mixture of toluene and removed under reduced pressure, but the odor of acetic acid all remains. All the material is dissolved in hot toluene (75 ml), and formed a cloudy solution, which is treated in the filter "DARKO" and filtered. After cooling pinkish solution to room temperature is highlighted white solid. After cooling in the freezer, the solid is collected by filtration, washed with hexane and dried on the filter. Further drying in a vacuum oven at 45aboutWith led to the product (1.2 g, SUB> Calculated: 41,20; 1,43 N; N 8,01; Br 22,89; Cl 10,16; F To 16.31; Found 41,27; N 1,48; N 8,10; Br 22,92; Cl 10,16; F 16,03.

By the synthesized appropriate 2-aryl-5-(trifluoromethyl) pyrrole-3-carbonitrile obtained by the procedure of example 57, respectively, the above recipe, prepare the following compounds (see table. 12).

P R I m e R 59. Obtaining 2-(4-chlorophenyl)-5-trifluoromethyl-pyrrole-3,4-dicarbo - nitrile.

Triperoxonane anhydride (3.1 ml; to 0.22 mole) is added with a single dose (4-chlorophenyl) glycine (2.0 g; to 0.011 mol), which causes an immediate yellow staining and slight appearance of phlegmy. The mixture is gradually heated to reflux, which causes dissolution of the material to yellowish-orange solution, which is optionally heated 2 hours the Reaction mixture is cooled and the solvent is removed under reduced pressure. Double-add toluene, followed by its removal under reduced pressure, resulting in a very thick oil (Vco=1800 cm-1). This residue is dissolved (is a certain amount of undissolved material) in nitromethane (40 ml) and add bromomalonate (2.7 g; 0,018 mole) in a single portion. The resulting solution was heated under reflux for 18 h, giving temnerature quantity of insoluble substances are removed by filtration.

Material fractionary by dry column chromatography (silica gel, 3% 2-WG OH in dichloromethane) and select the appropriate faction. The evaporation of one faction leads to the target compound as a yellow solid, which is recrystallized from nitromethane (processing DARKO), which gives a pale-yellow solid (0.2 g), so pl. 238-241aboutWith some decomposition).

P R I m e R 60. p-Chloro - a -(formylmethyl)amino/nitrile cinnamic acid, diethylacetal.

Stir magnetic stirrer, a solution of 250.0 g (1,39 mole) p-chlorbenzoyl acetonitrile, 203 ml (185,9 g; 1,39 mole) 2,2 diethoxyaniline and 1300 ml of dried toluene is heated under reflux for 20 hours Water (23,8 ml; 95.2% of theory) is collected in the trap Dean-stark. Hot, muddy dark brown solution with a large amount of undissolved solids filtered off, using hard-shelled land as an aid. After dilution with 200 ml of ethyl acetate, the solution is filtered through a 7 SMH,5 cm column of silica gel. The filtrate was concentrated in vacuo, giving 354,3 g (86.4% of the yield of the crude substance) clear dark oil that slowly solidified. This solid precrystallization showed the presence of isomeric mixture of 78% (Z) and 23% (E) p-chloro - a -(formylmethyl)amino/nitrile cinnamic acid, diethylacetal, so pl. 60-72aboutC.

Following the above procedure, however, when replacing the proper benzoylacetonitrile p-chloro-benzoyl acetonitrile and/or appropriate 2,2-di(C1-C4alkoxy) ethylamine 2,2-diethoxyaniline get the following compounds (see table. 13).

P R I m e R 61. 2-(p-chlorophenyl)-pyrrole-3-carbonitrile.

To 108 ml triperoxonane acid mixed with 23aboutTo add 54,00 (0,183 mole) of solid p-chloro - a- (formyl-methyl)amino)cinnamic nitrile diethylacetal for more than 45 m This addition leads to a temperature rise up to 38aboutDuring the exothermic reaction and through 32 m during the add starts the deposition of solids. After 30 m of stirring at room temperature the reaction mixture is filtered under vacuum and collected solid is washed first with triperoxonane acid, then with a mixture of ethyl acetate with hexane, and finally with hexane. The output is not quite white solid substance was equal to 16.83 g (45,4%), so pl. 165-166aboutC.

Using the above procedure, but replacing conc. hydrochloric acid triperoxonane acid is obtained the following compounds (see table. 14).

P R I m e the mole) of 2-(p-chlorophenyl) pyrrole-3-carbonitrile in 450 ml of glacial acetic acid at the 36aboutTo add drops of 14.7 ml (24,70; USD 183.0 mmole Sulfuryl chloride for 18 PM Adding accompanied by a slight exotherm raising the temperature to 39aboutC. After an additional 16 m, the reaction mixture was filtered in a vacuum. The collected solids washed first with acetic acid, then water. This solid after recrystallization from hot ethyl acetate has so pl. 259-261aboutC.

P R I m e R 63. 4,5-dibromo-2-( - Cryptor-p-tolyl)pyrrole-3-carbonitrile.

To a stirred mixture of 0.8 g of 2-( -p-tolyl)pyrrole-3-carbonitrile in 70 ml of chloroform is added 2 ml of bromine. From the mixture after stirring overnight falls white solid, which was collected by filtration. Thin layer chromatography (1:1 ethyl acetate-hexane) showed the presence of only one component, so more than 230 squareaboutC.

By following the above procedure, but substituting the appropriate substituted, phenylpyrrole-3-carbonitrile 2 ( -Cryptor-p-tolyl)pyrrole-3-carbonitrile obtain the following compounds (see table. 15).

P R I m e R 64. -(2,2-diethoxyaniline)- -nitrostyrene 3-nitro-2-phenylpyrrole. Alpha-nitro acetophenone (5.7 g; 0,0345 mole) is introduced into 100 ml of toluene and added 4.6 g (0,0345 mole) amino acetaldehyde demolecularize sieves 4A. The mixture is heated under reflux for 18 hours, the Toluene is removed in vacuo, giving at 8.36 g -(2,2-di amoxicillin)- -nitrostyrene in the form of a brown oil. To this oil is added 50 ml of concentrated hydrochloric acid. As the mixing flask rotation oil goes in a yellow suspension. After 10 m the solid is filtered off, giving 2,48 g yellow solid. Recrystallization from ether (ethyl acetate) hexane gives 2 fraction of the product: 2,08 g so pl. 190-192about(31%).

Max. 1485 cm-1(NO2);

H-NMR (deuterated chloroform/dimethyl sulfoxide). of 6.73 (multiplet, 2H); 7,46 (multiplet, 5H).

Other derivatives nitrostyrene can be prepared by the above reaction by substitution of nitro acetophenone appropriately substituted-nitro-acetophenone and/or amino of acetylcholinesterases appropriate 2,2-di(C1-C4-alkoxy) ethylamine, which leads to the following compounds (see table. 16).

P R I m e R 65. 3-dichloro-4-nitro-5-phenylpyrrole.

A mixture of 3-nitro-2-phenylpyrrole (1.56 g; 0,0083 mol) in 60 ml of dioxane is cooled in an ice bath as you add drops of 25.9 g (0,0182 mole) of a commercially available sodium hypochlorite. After 45 m peremeshivaniem and the upper organic washed with water, dried over anhydrous magnesium sulfate and concentrated in vacuo, giving 2,21 yellow solid. Cleaning chromatographytandem using silica gel and a mixture of ethyl acetate with hexane in a growing relationship for removal with adsorbent gives, after steaming, of 0.77 g of yellow solid (36%), so pl. 190-190,5aboutC.

P R I m e R 66. Obtain 3-cyano-2-(3,4-dichlorophenyl)-N,N-dimethylpyrrole-1-CT - oxamide.

A solution of 2-(3,4-dichlorophenyl)-pyrrole-3-carbonitrile (10.0 g, 0,0422 mole) in tetrahydrofuran was treated with tert-piperonyl potassium (13,2 g, 0,1176 mole), was stirred at room temperature for one hour, then was treated with chloride dimethylcarbamyl (13,2 ml, 15,31 mole), was stirred at room temperature for 16 h, treated with additional portions of tert-butoxide potassium (4.4 g, 0,0392 mol) and chloride dimethylcarbamyl (4,4 ml, 5,104 mol), was heated at a temperature of condensing in the reflux for one hour, cooled to room temperature and poured into ethyl acetate and water.

The phases were separated and the organic phase is washed with water, dried over anhydrous magnesium sulfate and concentrated in vacuo to education oily residue. Oily imesi diethyl ether with hexane composition of 50:50, the result has been named product as white matter weight of 4.7 g (yield 36%) with T. pl. 120-122aboutC.

P R I m e R 67. Obtaining N,N-dimethyl-2,3-dibromo-4-cyano-5-(3,4-dichlorophenyl) pyrrole-1-carboxamide.

A solution of N, N-dimethyl-3-cyano-2-(3,4-dichlorophenyl)pyrrole-1-carboxamide, taken in an amount of 1 g in tetrahydrofuran was treated with bromine, taken in an amount of 3.8 g, was stirred for five days and then concentrated in vacuum, obtaining a remainder of brown oily liquid. The liquid was purified by chromatography using silica gel and as eluent a mixture of simple ether with hexane at a ratio of 1:1, resulting in the received semi-solid substance, which is extruded on a clay plate with the formation of the named product as white solids, the amount of which was 0.45 g; so pl. 144-149aboutC.

P R I m e R 68. Getting 4-bromo-1-(methyl bromide)-2-(p-chlorophenyl)-5-(triptime - Tyl)pyrrole-3-carbonitrile.

A solution of 4-bromo-2-(p-chlorophenyl)-1-(methyl)-5-(trifluoromethyl)-pyrrole-3-carbonita - Rila (30 g, 0.0825 g mole) in carbon tetrachloride (450 ml) was treated with bromine (13,2 ml of 18.8 g) was subjected to photolysis, affecting light from a mercury arc lamp in photochemic mol), and the irradiation was continued for 47 hours, the Reaction mixture is subsequently washed with an aqueous solution of metabisulfite and water and concentrated in vacuum, obtaining a solid substance. This solid is triturated with carbon tetrachloride (50-60 ml) and heptane (100 ml) and filtered, obtaining the named product as a white solid (18.3 g, so pl. 131-131,5aboutC).

P R I m e R 69. Getting 4-bromo-2-(p-chlorophenyl)-1-(ethoxymethyl)-5-(triptime - Tyl)pyrrole-3-carbonitrile.

To 1000 ml of dry tetrahydrofuran was added 130, 8mm g of 4-bromo-2-(p-chlorophenyl)-5-(trifluoromethyl)pyrrole-3-carbonitrile. The mixture was stirred, and there several portions were added to 43.3 g of tert-butoxide potassium, which led to the occurrence of an exothermic reaction. Temperature control of an exothermic reaction was carried out by cooling the reaction flask in a water bath.

To stir a mixture of the two portions was added 36.5 g simple chloromethylation ether. Then over the course of the reaction was monitored by conducting thin-layer chromatography.

After about four hours the reaction mixture was diluted with 300 ml of simple ether and washed with dilute hydrochloric acid and water. The organic phase by tdeprecated from 500 ml of isopropyl alcohol was obtained 102 g of the named product, colourless solid with so pl. 99-100aboutC.

P R I m e R 70. Obtain 4,5-dichloro-2-(3,4-dichlorophenyl)-1-(1-ethoxy-ethyl) - pyrrol-3-carbonitrile.

To 4,5-dichloro-2-(3,4-dichlorophenyl)pyrrole-3-carbonitrile (5.0 g, to 0.016 mol) dissolved in 300 ml of tetrahydrofuran, portions were added tert-piperonyl potassium (2,75 g 0,025 mol), making it with ice cooling, and stirred. The cooled mixture was treated with a solution of a simple 1-chloramination ether (2,31 g 0,021 mol) in 15 ml of tetrahydrofuran at 10aboutWith over a period of time in 5 minutes and the Mixture was stirred for 30 min at ambient temperature, evaporated to a volume of 50 ml and poured into a mixture of 200 ml of ethyl acetate and 100 ml of water. The organic layer was separated, washed with water (2 times 100 ml), was affected by sodium chloride solution (1 x 100 ml), dried over anhydrous magnesium sulfate and was evaporated to obtain the titled product, the amount of which was 5.9 g; so pl. 124-126aboutC.

P R I m e R 71. Obtaining p-chloro-N-[(phenylsulfonyl)methyl]thiobenzamide.

Benzosulfimide sodium (17 g, 0.1 ml) was dissolved in 100 ml of water and treated with an aqueous solution of formaldehyde (3.2 g, 0, 11 mol, 37%) and sludge from the p-chlorobenzamido the mixture was cooled. A solid substance was separated by dumping was over it liquid; the solid is then treated with ethyl acetate, dried over magnesium sulfate and concentrated in vacuum, obtaining 20.7 g (yield 64%) of yellow solid. A portion of this solid (17 g) was recrystallized from methanol, gaining 6.7 g yellow solid, which was then purified into a slurry in hexane solution in ethyl acetate, taken in the ratio of 75:25, resulting in the received product named in the amount of 5.7 g with a yield of 20.9% so pl. 145-150aboutC.

P R I m e R 72. Obtaining methyl-p-chloro-N-[(phenylsulfonyl)methyl]thiobenzamide.

A solution of p-chloro-N-[(phenylsulfonyl)methyl]thiobenzamide (1.0 g, of 0.003 mol) in methylene chloride was cooled below 10aboutWith, were treated with methyltrichlorosilane (0,57 g, 0,0035 mole), was stirred for three hours at a temperature of less than 10aboutC and for 16 h at room temperature and was filtered. The filtrate is then washed with water and with dilute potassium carbonate solution, dried over magnesium sulfate and concentrated in vacuum, obtaining an oily residue, which was utverjdala. The residue was subjected to evaporative chromatography using methylene chloride, and C is Tate which has been named product as white solids, the number of which amounted to 0.4 g at the exit 40% so pl. 120-123aboutC.

P R I m e R 73. Obtain 2-(p-chlorophenyl)-4-(trifluoromethyl)pyrrole-3-carbonita - Rila.

A mixture of dimethoxyethane (15 ml) and dimethyl sulfoxide (5.5 ml), was treated with 60% sodium hydride (0.28 g). Then all at once was added to a solution of methyl-p-chloro-N-[(phenylsulfonyl)methyl] thiobenzamide (1.07 g, of 0.003 mol) and 3,3,3-crittertrail (0.45 g with a content of pure substance 85%) dimethoxyethane. (Watched the gas and raising the temperature to 30aboutC due to the exothermic reaction). The reaction mixture is kept at 30aboutC, cooled to room temperature, was stirred for 90 min, then poured into water (100 ml) and acidified to pH 16 N. hydrochloric acid. The precipitation was filtered and dissolved in a simple ether. The ether solution was dried over magnesium sulfate and concentrated in vacuum, obtaining a brown solid residue. The solid was purified into a slurry when mixed with a small amount of methylene chloride (10 ml), and filtered, obtaining 0.39 g of the named product; so pl. 225-228aboutC.

P R I m e R 74. Getting 5-bromo-2-(p-chlorophenyl)-4-(trifluoromethyl)pyrrole-3-CT - Bonita balali to a solution of anhydrous sodium acetate (0.21 g, 0,0025 mol) in acetic acid was treated with a solution of bromine (0.26 g, 0,0016 mol) in acetic acid was stirred overnight at room temperature and poured into water. The resulting mixture was filtered, highlighting the named product as a white solid (0,423 g) so pl. exceeding 230aboutC.

P R I m e R 75. Getting ethyl-2-(3,4-dichlorophenyl)-4,4,4-triftoratsetata.

A suspension of 60% sodium hydride (7.0 g, 0,18 mol) in 200 ml of tetrahydrofuran and 200 ml of diethyl ether was treated dropwise with a solution of ethyl-4,4,4-triftoratsetata (26,8 g, 0,146 mol) in 100 ml of tetrahydrofuran, stirred at room temperature for 45 min, cooled to 5-10aboutand was treated with a solution of 2-bromo-3' 4' -dichloroacetophenone (39,1 g, 0,146 mol) in 200 ml of tetrahydrofuran over a period of time in 20 minutes the Reaction mixture was allowed to warm to room temperature, it was heated in a vessel under reflux for five days, cooled to room temperature and was slowly treated with 200 ml of water. The phases were separated, and the organic phase washed with water (4 x 200 ml) and brine (100 ml), dried over magnesium sulfate and concentrated in vacuum, obtaining a viscous oily liquid, which was aterials with so pl. 95-98aboutC. This substance is directly used in the implementation of the subsequent methods.

P R I m e R 76. Obtaining 3'4' -dichloro-4-oxo-5,5,5-triptoreline.

A mixture of ethyl-2-(3,4-dichlorophenyl)-4,4,4-triftoratsetata (20 g, 0,054 mole) in water, acetic acid and sulfuric acid (300 ml, 300 ml, 60 ml, respectively) was heated in a vessel under reflux for 15 hours, watching the emissions of carbon dioxide,cooled to room temperature and neutralized by slowly adding solid sodium bicarbonate. The reaction mixture was filtered, and the filter cake was dissolved in 300 ml of ethyl acetate, dried over sodium sulfate and concentrated in vacuum, obtaining white solid. The solid was purified by vigorous mixing with cold hexane, resulting received the named product as white solids, the amount of which was 11 g; so pl. 97-99aboutC.

P R I m e R 77. Obtain 2-(3,4-dichlorophenyl)-5-(trifluoromethyl)pyrrole.

A solution of 3' 4' -dichloro-4-oxo-5,5,5-triptoreline (10.0 g, 0,033 mol) and ammonium acetate (7.7 g, of 0.10 mol) in glacial acetic acid (50 ml) was heated to 55-60aboutWith doing this in an environment Azeem stirring, and was treated with 300 ml of dimethyl ether. The phases were separated, and the organic phase is repeatedly washed with a saturated solution of sodium bicarbonate (to obtain a neutral aqueous leaching), then washed with brine, dried over sodium sulfate and concentrated in vacuo to obtain a dark red oily residue. Spending evaporative chromatography of the residue on silica gel using as eluent a mixture of hexane with ethyl acetate, taken in the ratio of 6:1 has been named the product (7.0 g, yield 75%) as a red oily liquid.

P R I m e R 78. Obtain 2-(3,4-dichlorophenyl)-3-nitro-5-(trifluoromethyl)-pyrrole.

A solution of 2-(3,4-dichlorophenyl)-5-(trifluoromethyl)pyrrole (4.0 g, to 0.016 mole) in acetic anhydride (30 ml) was treated dropwise at temperatures in the range from 25 to 30aboutWith 90% fuming nitric acid (0,86 ml 0,018 mol). The reaction mixture was stirred for 30 min at 30-40aboutC, was poured into 300 ml of water and stirred until the occurrence of the hydrolysis of acetic anhydride. The aqueous layer was decanted from the semi-solid substance, which translated into a simple ether, dried over magnesium sulfate and concentrated in vacuum, obtaining a brown semi-solid residue, which was turned into sludge, D. who was alocale named substance in the form of a yellow solid with so pl. 154-156aboutC.

P R I m e R 79. Obtain 3-bromo-5-(3,4-dichlorophenyl)-4-nitro-2-(trifluoromethyl)PI - role.

A solution of 2-(3,4-dichlorophenyl)-3-nitro-5-(trifluoromethyl)pyrrole (1.6 g, of 0.005 mol) in dioxane was treated with a solution of bromine (0,98 g 0,006 mol) in dioxane, stirred overnight and concentrated in vacuo to education oily residue. The residue was subjected to separation between the simple ether and water. The ether layer was separated, dried over magnesium sulfate and concentrated in vacuo to education oily liquid, which gradually aterials with the formation of a yellow solid. By recrystallization of the solid substance from a mixture of benzene and hexane received the named compound as a dark yellow solid with so pl. 154-156aboutC.

P ri m e R 80. Obtain 2-(p-chlorophenyl)-3,5-bis(trifluoromethyl)pyrrole.

A solution of 3.0 g of 4-p-chlorophenyl-2-(trifluoromethyl) oxazoline-5-she and 2.0 g of 2-bromo-3,3,3-triptocaine in acetonitrile was treated with 1.2 g of triethylamine was heated at the temperature of condensing in the reflux for one hour and concentrated in vacuum to form a residue. The residue was subjected to chromatography on silica gel using the mixture of hexanchidae substances in amount of 1.6 g so pl. 41-43aboutC.

P R I m e R 81. Obtain 2-(p-chlorophenyl)-4-nitro-3,5-bis(trifluoromethyl)-Pirro - La.

A solution of 0.74 g of 2-(p-chlorophenyl)-3,5-bis(trifluoromethyl)pyrrole in acetic anhydride was treated dropwise to 0.68 ml of 90% nitric acid, was stirred over night at room temperature, was heated up to 35-38aboutC and kept at this temperature for 1 h and poured into water. The mixture was extracted with simple ether. The ether extracts were combined, dried over magnesium sulfate and concentrated in vacuum to form a residue. The residue was subjected to chromatography on silica gel using mixtures of hexane with ethyl acetate, taken in the ratio of 4:1, resulting in a received product named in the form of a white solid substance, the amount of which was 0.27 g, and so pl. was 140-143aboutC.

P R I m er 82. Obtain 1-(3,4-dichlorophenyl)-4,4,4-Cryptor-1,3-butandione.

A suspension of sodium hydride (60% suspension in mineral oil, 5.0 g, a 0.125 mol) in tetrahydrofuran was heated to 40aboutC was treated dropwise with a solution of 3' 4' -dichloroacetophenone (15.0 g, 0.079 in mol) and ethyltryptamine (11,28 g 0,079 mol) in tetrahydrofuran, stirred for 2 h at 40aboutWith that processed the reduction of the original volume and diluted with water. The mixture was extracted with a mixture of hexane with simple ether, taken up in 1:1 ratio. The organic extracts were combined and extracted with water. All aqueous phases were combined, acidified to pH 1 with concentrated hydrochloric acid and was extracted with ethyl acetate. The organic phase was separated, washed successively with water and saturated sodium chloride solution, dried over anhydrous magnesium sulfate and concentrated in vacuum to the formation of the named product as a viscous amber oily liquid obtained in the amount of 15.3 g

P R I m e R 83. Getting ethyl-1-cyano-N-[2-(3,4-dichlorobenzoyl)-1-(trifluoromethyl)vinyl]glycinate.

A mixture of ethyl-2-cyanopyridine (10 g, 0,078 mol) and 1-(3,4-dichlorophenyl)-4,4,4-Cryptor-1,3-butadiona (18 g, 0,063 mole) in benzene was heated at a temperature of condensing in the reflux (using the trap Dean Starks (Dean Stark) for removal of water) for 4 h the Reaction mixture was concentrated until the formation of brown solid residue, which was turned into a slurry by mixing with hexane, and filtered. The filter cake was washed with cold simple with ether, and dried in the air, getting named product as colorless solids, the amount to which phenyl)-5-(trifluoromethyl)pyrrol-2-Carboni - trile.

A mixture of ethyl-2-cyano-N-[2-(3,4-dichlorobenzoyl)-1-(trifluoromethyl)vinyl]glycinato (2 g of 0.005 mol) and triperoxonane acid (75 ml) was heated at a temperature of condensing in the reflux for 8 h, then poured onto ice and filtered. White solid filter cake was dried and subjected to chromatography on silica gel using a mixture of hexanol with ethyl acetate (taken in the ratio 5: 1), resulting in the received named product as colorless solids with so pl. 215-216aboutC.

P R I m e R 85. Getting 4-bromo-3-(3,4-dichlorophenyl)-5-(trifluoromethyl)-pyrrole-2-carbonitrile.

A solution of 3-(3,4-dichlorophenyl)-5-(trifluoromethyl)pyrrol-2-carbonitrile (1 g, of 0.003 mol) in tetrahydrofuran was treated with N-bromosuccinimide (0,76 g of 0.004 mole), was stirred for 1 h and was poured into a mixture of water and ethyl acetate. The organic phase was separated, then washed with water and saturated sodium chloride solution, dried over anhydrous magnesium sulfate and concentrated in vacuo to education yellow solid. By recrystallization from toluene has been named product as a white solid weighing 0.4 g with so pl. 175-178aboutC.

P R I m e R 86. Getting 4-bromo-3-(3,4-dichlorophenyl)-2-(ethoxymethyl)-5-(is itril (1.0 g, of 0.003 mol) in tetrahydrofuran was treated with portions of tert-butoxide potassium (0.4 g, 0,004 mol), after which impacted simple chloromethylation ester (0.4 g, of 0.004 mol) in tetrahydrofuran, stirred overnight at ambient temperature and was poured into a mixture of water with ethyl acetate. The layers were separated; the organic layer was sequentially washed with water and saturated sodium chloride solution, dried over anhydrous magnesium sulfate and was evaporated to education amber semi-solid residue. The residue was turned into a slurry by mixing with hexane, and filtered, getting named product as white solids weight of 0, 61 g so pl. 98-101aboutC.

P R I m e R 87. Following the procedure described in example 74 but using the appropriately substituted phenylpyrrole-3-carbonitrile or 3-nitro-2-(substituted)phenylpyrrole and appropriate alkylating agent was obtained compounds are shown below (see tab. 17 and 18).

P R I m e R 88. Bralirwa appropriate 2-aryl-5-(trifluoromethyl)pyrrole-3-Carboni - home to the thrill obtained by the method of example 57 according to the procedure of example 58, additionally received the following compounds (table. 19).

P R I m e R 89. Using the proper eilperin in the method of example 5">

P R I m e R 90. Evaluation of the insecticidal and acaricidal action.

All tests are prepared in advance with the use of technical materials. All concentrations given here are expressed in units of the active ingredient. All tests are conducted at the 27aboutC.

Spodoptera eridania Mealybug South on 3 stages of development of larvae, leaf bean semicircular lim, stretching to 7-8 cm in length, immersed in the test suspension under stirring for 3 seconds and placed under the hood to dry. Then the sheet is placed in a Petri dish 100x100 mm, containing at the bottom of moistened filter paper and 10 caterpillars on 3 stages. Cup stand 5 days prior to conducting observations over the loss, decreased ability to eat or for any deviation from the normal state.

Spodoptera eridania, 7 days remaining.

Plants treated according to the above test, is kept in a greenhouse under lamps high intensity 7 days. These lamps repeat the influence of a bright Sunny day in June in new Jersey and is maintained at a day length of 14 hours After 7 days the leaves are collected and evaluated according to the above test.

Aphis fabae mixed stage of development, aphids Bob the aphids for 1 day before testing. Each pot sprayed with a test formulation at 2 sudden changes in rotation at 4 rpm around the stem. For spraying, use a spray De-Vilbiss N 154. The tip of the nozzle is kept at a distance of about 15 cm from the plant and sprayed liquid is directed in such a way as to ensure full coverage and plants and aphids. Opalanie pots set on the walls of the white enamelled shelves and hold for 2 days, after which establish the extent of killing.

Tetra nychus urtica (R-resistant species), 2-spotted spider mite (see tab. 21).

Bean plant semicircular lim primary leaves, blown up to 7-8 cm, choose and cut so that there is 1 plant in each pot. A small piece cut from a sheet taken from the main colony, and placed on each sheet of the tested plants. Do this for about 2 h before treatment, to allow the clamp to move around the subject plant and lay eggs. The size of the cut piece of change so that to get about 100 ticks on 1 sheet. At the time of processing a piece of sheet, used for transferring mites, remove and discard. Plants infected ticks, dipped 2 days to establish a dead adult, using the first sheet. The second sheet remain on the plant for another 5 days until the next observation atrophy of the testicles and/or newly hatched larvae.

Diabrotic undecimpunctata howardi, root worm South, 3 age stage of development of the worm.

1 cm3finely ground talc is placed in a 30 ml glass jar with a wide mouth and screw cap. 1 ml of the appropriate acetone suspension is served by pipette on talc so that in each Bank to ensure the availability of 1.25 and 0.25 mg of the active ingredient. Banks placed under conditions of gradually moving air stream until you evaporate the acetone. The dried talc free and add 1 cm3seeds of millet to provide forage for insects. Then in each jar contribute 25 ml of moist soil. Close a jar lid and the contents thoroughly mixed in the mixer "Vortex". Then in each jar contribute 10 root worms in 3 stages of development banks and loosely covered with a lid to provide ventilation for the larvae. Treatment continued for 6 days before you start counting dead animals. Missing larvae (caterpillars) was assumed to be lost due to rapid decomposition, so they were not aldarondo.

Evaluation scale:

0 no action

1 10-20% loss

2 20-35% death

3 36-45% death

4 46-55% death

5 56-65% death

6 66-75% death

7 75-85% death

8 86-99% death

9 100% killing

R reduced perception of food.

P R I m e R 91. Evaluation of insecticidal action.

liothis virescens 3-age stage of development of the larvae mealybug tobacco kidney.

Sameday cotton is dipped in the test formulation and leave to dry under the hood. After drying, each cut into 4 pieces and 10 sections, each separately placed in a 30 ml plastic medical cups 5-7 mm long pieces of moistened dental swab. In each Cup put a caterpillar in 3 stages of age development and cover the cardboard Cup loosely. Processing can withstand 3 days, before proceeding to the calculation of the degree of destruction and determine the extent of reducing damage to the feed.

Empoasca abrupta, adult, leaf potato flea West.

Bean leaf varieties Sieva lima about 5 cm in length is dipped in the test formulation 3 with under stirring and place under the hood to dry. The sheet is placed in a Petri dish, containing at the bottom of the wet filtroval the estimation of the degree of destruction.

Blatella germanica test with bait, adult male cockroach German (Prussian). 0,1% bait is prepared by measuring pipette 1 ml of 1000 ppm of the test compound in acetone and applying this solution to 1 g of corn flour, with a subsequent payment in 30 ml wide-mouthed jar. Bait dried careful transmission of air into the jar. The bait is placed in a 0.6 liter wide-mouthed jar of Mason and make 10 adult male cockroaches. Close a jar with a mesh lid. On the upper part of the mesh cover, put the jar on top of a mesh cover, put a small piece of cotton soaked in 10% honey solution. After 3 days start to count the deaths.

Blatella germanica final test, the adult males of the cockroach German (Prussian).

1 ml of 1000 parts per million acetone solution of the test material gradually make the eyedropper on the bottom h mm Petri dishes in such a way as to provide uniform coverage. After drying the deposited material in each Cup placed 10 adult male cockroaches and close the lid. After 3 days start to count the deaths.

Spodoptera eridania systemic effects, stage 3 age development gusii, containing 0.1 g of the test material; 0.2 g of emulsifier "Emulphor El-620; 10 ml of acetone and 90 ml of water. It is diluted 10-fold with water to obtain 100 parts per million emulsion for testing. Then, as necessary, prepare 10-fold dilution with water. Legumes Sieva lima with the primary leaf length of 7-8 cm is cut at the level of at least 3 cm above the soil surface. Do avoid contamination contained in the soil bacteria that will cause damage to the stem during the test. Cut stems are placed in the subjects of the emulsion and each stem is wrapped with a piece of wool to maintain the stem on top of the bottom of the banks, as well as to limit evaporation and volatility compounds. The test continued for 3 days at 27aboutTo provide the perception of plant compounds. Then 1 sheet is removed from the plant and placed h mm Petri dish with 10 likuidasi single point (the scale). Tests on the degree of destruction and monitoring damage to forage spend 3 and 5 days later.

Empoasca abrupta systemic exposure, adult leaf potato flea West.

Connection enter the formula in the form of an emulsion containing 0.1 g of the test material; 0.2 g of among the Lyon for testing. Then, as needed, prepare 10-fold dilution with water. Plant beans "Sieva lima", primary leaves which extend at 7-8 cm, cut at the level of at least 3 cm above the soil surface. Do avoid contamination contained in the soil bacteria that will cause damage to the stem during the test. Cut stems are placed in the subjects of the emulsion and each stem is wrapped with a piece of wool to maintain the stem on top of the bottom of the banks, as well as to limit evaporation and volatility compounds. The test continued for 3 days at 27aboutTo provide the perception of the compounds of plants. Following this, 1 sheet removed from the plants and placed in h ml Petri dish, and keep the definition as stated above. Evaluation scale for the above tests is the same as described in example 90 (see tab. 22).

P R I m e R 92. A) Evaluation of the tested compounds as nematicide funds.

The content of culture: Culture of C. elegans (Bristol strain from j. Lewis) are maintained in E. coli areas agar plates at 20aboutC. New cultures are set weekly.

Nematodes for testing out of cultures in the age of 4-5 days using fresh rastvoryeniya and centrifuged to separate the worms from the leaching solution. This procedure was repeated three times. Then washed worms add to C. briggsae environment to maintain them (SWMM) from GIBCOa, to which add gentamicin (600 units/ml) and mycostatin ( 0.5 mg/ml).

Then carry out tests with mixtures of three compounds piggy backed from another program scilingo with high performance, to reduce additional labor costs and expenses of connection.

Compounds are dissolved in acetone and brought to volume by equal volumes of water. For a final test concentration of each compound in a mixture of 150 parts per million. The tested material is served by using the pipettor (25 ál) in each individual cell plates with sterile tissue culture containing 96 wells (COSTAR)band the solvent allowed to evaporate. These "processed" vinyl use immediately or store in the freezer in the absence of obvious negative effects on the connection.

Freshly amount (50 μg) in C. elegans Swmm will micropipettor in each treated cell and a number of control cells in each plate. Plates containing the culture, incubated at 20aboutC.

Monitoring the effectiveness and efficiency produced under the analytical is of movement worms. Activity is judged subjectively, but half-quantitatively based on the action of matter on mortality of adults and larvae. Criteria are the following: 8 the lack of mobility; 7 significantly reduced ability to travel approximately 95% of the worms; 6 reduced mobility; 5 weakly reduced mobility; 0 normal mobility, the same as in the control experiment. Other factors, marking the activity, observe easily. These include the defeat of paralysis, abnormal twitching, reduced reproduction for 48 h and other deviations from normal behavior.

The procedure for testing CAENORHABDITIS ELEGANS

Day 0. Insulinopenia E. coli NG agar plates at 30-50aboutC.

Incubation at 20aboutC.

Day 4. The collection of new populations of C. Elegans.

Lavage with antibiotics.

Transfer to Swmm.

The addition of C. Elegans (25-100 UL) to the filled cellsa).

Monitoring activity to 4 h after immersion

Day 5. Monitoring activity

Day 6. Monitoring activity

Note: a) Filled cells can be prepared fresh or in advance if stored in the refrigerator.

Obtained in this the population of nematodes in root nodules (Meloidogyne incognita) support on the tomato variety "meteor" in the greenhouse. Mass of the testicles are removed from the infected root surfaces and keep on moistened filter paper for 48 h, to give them possibility. Hatched, the larvae fall into the water close to the paper. Larvae for testing transferred to the cell plate in a chamber containing compound at a concentration of 300 parts per million of 3% acetone in an amount of about 10 larvae. Infected cells incubated at 27aboutC. the Degree of mortification determined after 24 h after treatment. The data obtained are given in table. 23.

P R I m e R 93. Using the above compounds according to the invention is assessed against a range of insect species, including: sheet flea, mealybug renal tobacco, liquidy single point South and German cockroaches. The evaluation system is the same system that was used in the above examples. The data obtained are given in table. 24. In the event of two or more tests with the same test compound, one of the results is considered excessive. The symbol "-" in table. 24 shows a lack of testing.

As you can see from the data, the compounds of the invention are more effective insecticidal AG is sulprofos. The table shows that the compounds of the invention are more effective acaricidal agents against bimaculated spider mites (Tetranychus urticae) than standard commercial agents thiodicarb, amitraz and cypermethrin.

The test objects of the tables are defined below.

Test object the Scientific name

Bean Aphids Aphis fabae

Bean aphid Mixed age stage

SAW/Armyworms Spodoptera eridania

Larvae of the third age stage

P. Res.Mites, mites Tetranychus urticae

(R-resistant strain)

SCRW Diabrotic undecimpunctata howardi

3rd age stage 11 point

flea Howard

Leaf Hopper, Empoasa abrupta

Sheet Bloch Adult leaf fleas

Western potatoes

TBW3Heliothis virscens

3rd age stage of tobacco

leafroller

G. Cockroach Blattella germania

The Prussians Adult male German cockroaches

C. Ele Caenorhabditis elegans

Nematodes root growths Meloidogyne incognita

To translate the examples in kg/ha must be based on the applicable volume of insecticide, acaricide or nematocides solution for spraying. Typical volumes used for row crops are 200-500 l/ha, and for crops orchards 1250-4000 l/ha Then the concentration of the tion arylpyrol in ppm)

the concentration in kg/liter

As soon as it becomes known concentration in kg/l, the magnitude of the dose in kg/ha is determined by the formula:

(concentration arylpyrol in kg/l) (scope of application l/ha) dose of application in kg/ha

Using the above formula, determine dose in kg/ha (see table. 25).

As you can see from the above data, connection arylpyrol of the invention are effective insecticidal, acaricidal and nematocidal agents at doses of less than 4.0 kg/ha, with preferred doses are 0,125-4.0 kg/ha.

The Protocol insecticidal tests.

For measuring the toxicity of certain insecticides on the third stages of the tobacco leaf (Heliothis virescens) used the technique of immersion of the sheet. Cotton leaves dipped in insecticide solutions of acetone/water (50: 50) and then dried in air. Completely dry size 2,h,0 cm part of the treated sheet is placed in a gel-like carrier cell containing wet dental cotton swab of cotton fiber and the test object (third instar budworm). Cell covered with a sheet of Mylar and sealed with a hot iron. Mortality of larvae assessed at 72 h after treatment. probit analysis to obtain values LC50(lethal concentration 50%). The results are shown in table. 26.

The Protocol acaricide tests.

Tests conducted to determine the toxicity of some acaricidal compounds on bimaculated spider mites (Tetranychus urtica). Infested with ticks leaves lima beans (still connected to the plant) is dipped for three seconds acaricide in solutions of acetone/water (50:50). The treated plants are then kept in laboratory conditions at a constant temperature 27aboutC and relative humidity of 60%, the mortality rate of adult ticks define three days after treatment. Data mortality adult ticks were subjected to probit analysis to obtain values LC50(lethal concentration 50%). The results are shown in table. 27.

4,5-Dichloro-2-phenylpyrrole-3-carbonitrile

4,5-Dichloro-2-(p-chlorophenyl)-pyrrole-3-carbonitrile

4,5-Dichloro-2-(3,4-dichlorophenyl)pyrrole-3-carbonitrile

4,5-Dichloro-2-(p-(triptoreline)phenyl-pyrrol-3-carbonitril

4,5-Dichloro-2-(o-chlorophenyl)pyrrole-3-carbonitrile

2-(p-bromophenyl)4,5-dichlorprop-3-carbonitril

4,5-Dichloro-2-( -Cryptor-p-tolyl)pyrrole-3-carbonitrile

4,5-Dibromo-2-(o-chlorophenyl)pyrrole-3-carbonitrile

4,5-Dibromo-chlorphenyl)pyrrole-3-carbonitrile

4,5-Dibromo-2-(2,4-dichlorophenyl)-3-carbonitril

4,5-Dichloro-2-(m-chlorophenyl)pyrrole-3-carbonitrile

2,3-Dichloro-2-nitro-5-phenylpyrrole

2,3-Dichloro-5-(p-chlorophenyl)-4-nitropyrrole

2,3-Dibromo-5-(p-chlorophenyl)-4-nitropyrrole

2,3-Dibromo-4-nitro-5-phenylpyrrole

2,3-Dichloro-5-(3,4-dichlorophenyl)-4-nitropyrrole

2-(p-bromophenyl)-4,5-dichloro-3-nitropyrrole

2,3-Dichloro-4-nitro-5 - (trifter-p-olyl)pyrrol

T a b l I C and 22

4,5-Dichloro-2-phenylpyrrole-3-carbonitrile

4,5-Dichloro-2-(p-chlorophenyl)-pyrrole-3-carbonitrile

4,5-Dichloro-2-(3,4-dichlorophenyl)-peril-3-carbonitril

4,5-Dichloro-2-(p-triptoreline)phenyl-pyrrol-3-carbonitril

4,5-Dichloro-2-(o-chlorophenyl)-pyrrole-3-carbonitrile

2-(p-bromophenyl)-4,5-dichlorprop-3-carbonitril

4,5-Dichloro-2-( -Cryptor-p-tolyl)pyrrole-3-carbonitrile

4,5-Dibromo-2-(0-chlorophenyl)pyrrole-3-carbonitrile

4,5-Dibromo-2-(p-chlorophenyl)pyrrole-3-carbonitrile

4,5-Dibromo-2-( -Cryptor-p-tolyl)pyrrole-3-carbonitrile

4,5-Dichloro-2-(2,4-dichlorophenyl)pyrrole-3-carbonitrile

4,5-Dibromo-2-(2,4-dichlorophenyl)pyrrole-3-carbonitrile

4,5-Dichloro-2-(m-chlorophenyl)pyrrole-3-carbonitrile

2,3-dichloro-4-nitro-5-phenyl-pyrrol

2,3-Dichloro-5-(p-chlorophenyl)-4-nitrophila

2,3-Dibromo-5-(p-chlorophenyl)-4-nitropyrrole
-3-nitropyrrole

2,3-Dichloro-4-nitro-5- -Cryptor-p-tolyl)pyrrole.

T a b l I C and 23

4,5-Dichloro-2-(p-(triptoreline)phenyl-pyrrol-3-carbonitril

4,5-Dichloro-2-( -Cryptor-p-tolyl)pyrrole-3-carbonitrile

4,5-Dibromo-2-( -Cryptor-p-tolyl)pyrrole-3-carbonitrile

2,3-Dichloro-4-nitro-5-phenylpyrrole

2,3-Dichloro-4-nitro-5-phenylpyrrole

2,3-Dichloro-5-(p-chlorophenyl)-4-nitropyrrole

2,3-Dichloro-5-(3,4-dichlorophenyl)-4-nitropyrrole

2-(p-bromophenyl)-4,5-dichloro-3-nitropyrrole

2,3-Dichloro-4-nitro-5 - (trifter-p-tolyl)pyrrole

T a b l I C and 24

2,5-Dichloro-4-phenylpyrrole-3-carbonitril

2,3-Dibromo-4-nitro-5-phenyl-pyrrol

4-Chloro-2-(p-chlorophenyl)pyrrole-3-carbonitrile

4,5-Dichloro-2-(0-chlorophenyl)pyrrole-3-carbonitrile

5-Bromo-2-(p-chlorophenyl)-pyrrole-3-carbonitrile 4,5-Dichloro-2-(3,4-dichlorophenyl)-1-(ethoxymethyl)-pyrrol-3-carbonitril

4,5-Dichloro-2-(p-chlorophenyl)-1-methyl-pyrrole-3-carbonitrile

n-(4,5-dichloro-3-cyanoprop-2-Il Metalinvest

4,5-Dibromo-2-(3,4-dichlorophenyl)pyrrole-3-carbonitrile

4,5-Dichloro-2-( -Cryptor-m-tolyl)-pyrrole-3-carbonitrile

4,5-Dichloro-2-(3,4-dichlorophenyl)-1-ethyl-pyrrole-3-carbonitrile

4,5-Dichloro-2-(3,4-differenl)pyrrole-3-carbonitrile

4,5-Dichloro-2-(3,4-dichlorophenyl)-1-methylpyrrole-3-carbonitrile

4,5-Dichloro-2-(BR>4,5-Dichloro-2-(p-forfinal)pyrrole-3-carbonitrile

4,5-Dibromo-2-(3,4-differenl) pyrrole-3-carbonitrile

4,5-Dibromo-2-(p-forfinal)pyrrole-3-carbonitrile

4,5-Dibromo-2-(p-nitrophenyl)pyrrole-3-carbonitrile

4,5-Dichloro-2-(p-nitrophenyl)pyrrole-3-carbonitrile

1-Benzyl-4,5-dibromo-2-(alpha, alpha, alpha-Cryptor-p-tolyl)pyrrole-3-carbonitrile

4,5-Dichloro-2-(p-cyanophenyl)pyrrole-3-carbonitrile

4,5-Dibromo-2-(n-(methylsulphonyl)phenyl)pyrrol-3-carbonitril

4,5-Dibromo-2-(p-chlorophenyl pyrrol-3-carbonitril 4,5-Dichloro-2-(3,4-dichlorophenyl)-1-(2-(methylthio)ethyl) - pyrrol-3-carbonitril

1-Methyl-4,5-dichloro-2-(3,4-dichlorophenyl)-pyrrole-3-carbonitrile

4,5-Dichloro-1-methyl-2-(alpha, alpha-alpha-t riptor-p-tolyl)pyrrole-3-carbonitrile

5-Bromo-4-chloro-2-(p-chlorophenyl)pyrrole-3-carbonitrile

2,3-Dichloro-5-(3,4-dichlorophenyl)-1-ethoxymethyl)-4-nitropyrrole

4-Bromo-5-chloro-2-(p-chlorophenyl)pyrrole-3-carbonitrile

1-Benzyl-4,5-dichloro-2-(3,4-dichlorophenyl)pyrrole-3-carbonitrile

Ethyl 2,3-dichloro-5-(3,4-dichlorophenyl)-4-cyanoprop-1-acetate

4,5-Dichloro-1-(ethoxymethyl)-2-(alpha, alpha, alpha-Cryptor-p-tolyl)pyrrole-3-carbonitrile

3-Bromo-5-(3,4-dichlorophenyl)pyrrole-2,4-dicarbonitrile 4,5-Dichloro-2-(3,4-dichlorophenyl)-1-1-(2-PROPYNYL)pyrrole-3-carbonitrile

4,5-Dibromo-3-(p-x)pyrrole-3-carbonitrile

4,5-Dibromo-3-(p-chlorophenyl)-1-methylpyrrole-2-carbonitrile

2-Bromo-5-phenyl-pyrrol-3,4-dicarbonitrile

4-Bromo-2-phenyl-5-(trifluoromethyl)pyrrole-3-carbonitrile

2-(3,4-Dichlorophenyl)-5-Nitropyrrole-3-carbonitril

4-Bromo - 2-(3,4-dichlorophenyl)-5-nitropyrrole-3-carbonitril

2,4-Dibromo-5-phenylpyrrole-3-carbonitrile

2-(3,4-dichlorophenyl)-4,5-deoderant-3-carbonitril

2,3-Dibromo-5-(p-chlorophenyl)-1-ethoxymethyl-4-nitropyrrole

1-Benzyl-2,3-dibromo-5-(p-chlorophenyl)-4-nitropyrrole

2,3-Dibromo-5-(p-chlorophenyl) 1-methyl-4-nitropyrrole

4,5-Dibromo-2-(p-(triptoreline)phenyl)pyrrole 3-carbonitril 4,5-Dichloro-1-(ethoxymethyl)-2-(p-(triptoreline)phenyl)pyrrol-3-carbonitril

5-(P-chlorophenyl)pyrrole-2,4-dicarbonitrile

1-Benzyl-4,5-dichloro-2(p-(triptoreline)phenyl)pyrrol-3-carbonitril

4,5-Dichloro-2-(p-chlorophenyl)-1-(ethoxymethyl)pyrrole-3-carbonitrile

4,5-Dichloro-2-(3,4-dichlorophenyl)-1-(2-oxyethyl)pyrrole-3-carbonitrile

2-(P-chlorophenyl)-5-nitropyrrole-3-carbonitril

4-Bromo-2-(p-chlorophenyl)-5-trifluoromethyl) pyrrole-3-carbonitrile

4-Bromo-2-(p-chlorophenyl)-5-nitropyrrole-3-carbonitril

3-Bromo-5-(p-chlorophenyl)-pyrrole-2,4-dicarbonitrile

4,5-Dichloro-2-(3,4-dichlorophenyl)pyrrole-1,3-dicarbonitrile 1-((Benzyloxy)methyl)-4,5-dichloro-2-(3,4-dichloropheny the Nile)pyrrole-2,4-dicarbonitrile 4,5-Dichloro-1-((p-chlorophenoxy)methyl-2-(3,4-dichlorophenyl)pyrrole-3-carbonitrile

4,5-Dichloro-2-(3,4-dichlorophenyl)-1-(3-iodine-2-propanol) pyrrole-3-carbonitrile

5-(3,4-Dichlorophenyl)-4-nitro-pyrrole-2-carbonitrile

2,4-Dibromo-5-(p-chlorophenyl)pyrrole-3-carbonitrile

3-Bromo-5-(n-(triptoreline)phenyl)pyrrole-2,4-dicarbonitrile

3-Bromo-5-(3,4-dichlorophenyl)4-nitropyrrole)-2-carbonitrile 4-Bromo-2-(p-chlorophenyl)-1-methyl-5-(trifluoromethyl)pyrrole-3-carbonitrile

3,4-Dibromo-5-(3,4-dichlorophenyl)pyrrol-2-carbonitril

2-(3,4-Dichlorophenyl)-5-trifluoromethyl)pyrrole-3-carbonitrile

5-(Trifluoromethyl)-2-(alpha, alpha, alpha-Cryptor-p-tolyl)pyrrole-3-carbonitrile

2,5-Dibromo-4-(p-chlorophenyl)pyrrole-3-carbonitrile

3,5-Dibromo-4-(p-chlorophenyl)pyrrole-2-carbonitrile

2-P-tolyl-5-(trifluoromethyl)pyrrole-3-carbonitrile

4-Bromo-2-p-tolyl-5-(trifluoromethyl)pyrrole-3-carbonitrile 4-Bromo-2-(p-chlorophenyl)-1-(ethoxymethyl)-5-(trifluoromethyl)pyrrole-3-carbonitrile

4-Bromo-2-(3,4-dichlorophenyl)-5-(trifluoromethyl)pyrrole-3-carbonitrile

5(alpha, alpha, alpha-Cryptor-p-tolyl)pyrrole-2,4-di carbonitril

1-Methyl-3-(alpha, alpha, alpha-Cryptor-p-tolyl)pyrrole-2,4-dicarbonitrile

4-Bromo-5-(trifluoromethyl-2-(alpha, alpha, alpha-Cryptor-p-tolyl)pyrrole-3-carbonitrile

3-Bromo-1-methyl-5-(alpha, alpha, alpha-Cryptor-p-tolyl)pyrrole-2,4-dicarbonitrile

4,5-DIH the l) pyrrole-2,4-dicarbonitrile

T a b l I C and 25

T a b l I C and 26

T a b l I C and 27

1. Derivatives arylpyrol General formula

< / BR>
where X is chlorine, bromine, iodine or CF3;

Y is chlorine, bromine, iodine, CF3or CN;

W is CN or NO2;

And hydrogen, C1-C4-alkyl, unsubstituted or substituted with halogen, hydroxy, C1-C4-alkoxy, C1-C4-alkylthio or phenyl group, phenoxy or C1-C2-alkoxyphenyl group, C1-C4-carbalkoxy, C3-C4alkenyl, unsubstituted or substituted with one halogen, cyano, C3-C4-quinil, unsubstituted or substituted with one halogen, di(C1-C4)alkylaminocarbonyl,

L is hydrogen, fluorine, chlorine or bromine;

M and R each independently hydrogen, C1-C3-alkyl, C1-C3-alkoxy, C0-C3-alkylsulfonyl, cyano, fluorine, chlorine, bromine, iodine, nitro, CF3group R1CF2Z or R2CO, where Z is oxygen, R1fluorine or CHF2, R2- C1C3-alkyl, and when M and R are in adjacent positions, they, together with the carbon atoms which are linked, form a ring, where the group MR is-CH=CH-CH= CH-.

2. The method of obtaining derivatives of helper
where L, M, R and W are specified in paragraph 1 values are subjected to interaction with 2,2-di(C1C4-alkoxy)ethylamine obtained respectively -[2,2-di(C1- C4-alkoxy)ethylamino]-b-lanosterol or a -[2,2-di(C1< / BR>
C4-alkoxy)ethylamino] b nitrosothiol treated with a mineral or organic acid.

3. a [2,2-Di(C1- C4-alkoxy)ethylamino]-b-lanosterol or a -[2,2-di(C1WITH4-alkoxy)ethylamino] b-nitrosothiol General formula;

< / BR>
where L, M, R and W have the specified values.

4. The way to combat insects, nematodes and mites by their processing derived arylpyrol, characterized in that as arylpyrol used as a compound of General formula I (where the values of the radicals listed in paragraph (1) effective as.

 

Same patents:

The invention relates to fungicidal means with increasing synergy effect against plant diseases and against microorganisms on plant material for breeding, especially for seed

FIELD: organic chemistry, agriculture.

SUBSTANCE: invention relates to novel trifluoromethylpyrrole carboxamides of the formula (I):

wherein R1 means hydrogen atom (H), (C1-C4)-alkyl; R2 means (C1-C4)-alkyl, (C1-C4)-halogenalkyl, (C1-C4)-alkoxy-(C1-C4)-alkyl, cyano-group or (C1-C6)-alkylcarbonyl; A means the group of the formula:

, or wherein R3 means (C1-C6)-alkyl, (C1-C6)-halogenalkyl, (C2-C6)-alkenyl, (C3-C7)-cycloalkyl, (C1-C4)-alkyl-(C3-C7)-cycloalkyl, (C4-C7)-cycloalkenyl, (C1-C4)-alkyl-(C4-C7)-cycloalkenyl, phenyl, naphthyl or phenoxy-group, or substituted phenyl, or substituted phenoxy-group wherein substituted represent 1-3 groups taken independently among an order comprising halogen atom, (C1-C4)_alkyl, (C1-C4)-alkoxy-, cyano-group, (C1-C4)-alkylcarbonyl, (C1-C4)-halogenalkyl, (C1-C4)-halogenalkoxy-, methylenedioxy-, difluoromethylenedioxy-group or phenyl; R4 means hydrogen, halogen atom or (C1-C4)-alkyl; each among R5, R6 and R7 means (C1-C6)-alkyl. Compounds of the formula (I) are used for control of phytopathogen organisms or for prophylaxis in damaging cultured plants by these organisms.

EFFECT: valuable properties of compounds.

10 cl, 3 tbl, 1 sch, 12 ex

FIELD: organic chemistry, agriculture, insecticides.

SUBSTANCE: invention relates to a substituted anilide derivative of the formula (I): wherein R1 represents hydrogen atom, (C1-C6)-alkyl group; R2 represents hydrogen atom, halogen atom or halogen-(C1-C6)-alkyl group; R3 represents hydrogen atom, halogen atom, (C1-C6)-alkyl group, hydroxyl group or (C1-C6)-alkoxy-group; t = 1; m = 0; each among X that can be similar or different represents (C2-C8)-alkyl group, hydroxy-(C1-C6)-alkyl group or (C3-C6)-cycloalkyl-(C1-C6)-alkyl group; n = 1 or 2; Z represents oxygen atom; Q means a substitute represented by any of the following formulae: Q1-Q3, Q6, Q8-Q12, Q14-Q19, Q21 and Q23 (wherein each among Y1 that can be similar or different represents halogen atom, (C1-C6)-alkyl group, and so on); Y2 represents (C1-C6)-alkyl group or halogen-(C1-C6)-alkyl group; Y3 represents (C1-C6)-alkyl group, halogen-(C1-C6)-alkyl group or substituted phenyl group; p represents a whole number from 1 to 2; q represents a whole number from 0 or 2; r represents a whole number from 0 to 2. Also, invention proposes a chemical for control of pests of agricultural and fruit crops. The chemical comprises substituted anilide derivative of the formula (I) as an active component and represents insecticide, fungicide or acaricide. Also, invention proposes a method for addition of the chemical for control of pests of agricultural and fruits crops. Also, invention proposes aniline derivative represented by the general formula (II): wherein R1 represents hydrogen atom, (C1-C6)-alkyl group; R2 represents hydrogen atom, halogen atom or halogen-(C1-C6)-alkyl group; R3 represents hydrogen atom, halogen atom, (C1-C6)-alkyl group, hydroxyl group or (C1-C6)-alkoxy-group; t = 1; m = 0; each among X that can be similar or different represents (C2-C8)-alkyl group, hydroxy-(C1-C6)-alkyl group or (C3-C6)-cycloalkyl-(C1-C6)-alkyl group; n = 1 or 2. Invention provides the development of anilide derivative as insecticide, fungicide and acaricide against pests of agricultural and fruit crops.

EFFECT: valuable properties of compound.

5 cl, 6 tbl, 27 ex

FIELD: organic chemistry, herbicides.

SUBSTANCE: invention describes phenyl-substituted heterocyclic 1,3-ketoenols of the formula (I): wherein R1 and R3 mean independently of one another ethyl or (C1-C2)-alkoxy-group; Q means the group of the formula (Q1): or (Q2): wherein R4 and R5 in common with atoms to which they are joined form 5-7-membered cycle that can comprise additionally anellated alkylene chain consisting of 2-6 carbon atoms that, in turn, can comprise two heteroatoms taken among oxygen atom, and indicated cycle can be substituted with halogen atom, hydroxy-group, (C1-C6)-alkoxy-group, (C1-C6)-alkoxy-(C1-C6)-alkoxy-group, (C1-C4)-alkylcarbonyloxy-group, hydroxy-(C1-C4)-alkoxy-group, hydroxycarbonyl-(C1-C2)-alkoxy-group, methoxycarbonyl-(C1-C2)-alkoxy-group, methoxyimino-, methoxyethoxyethoxy-group; R6 and R7 means (C1-C10)-alkyl; R8 means hydrogen atom; X means oxygen atom; R20 means (C1-C10)-alkyl, and also agronomically acceptable salts and isomers of these compounds. Also, invention describes a method for preparing compounds of the formula (I), herbicide agent and a method for control of weed growth based on compounds of the formula (I). Invention provides preparing compounds possessing the herbicide activity.

EFFECT: improved preparing method, valuable properties of compounds and agents.

5 cl, 28 tbl, 5 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

FIELD: organic chemistry, agriculture.

SUBSTANCE: invention relates to incecticidal/acaricidal agent of synergetic action having general formula I wherein W, Y and Z are independently hydrogen or C1-C4-alkyl; A and B together with carbon atom to which they are bonded form C3-C6-cycloalkyl monosubstituted with C1-C4-alkoxyl; G is carbon or -COOR, wherein R is C1-C4-flkyl and compound selected from group containing chloropyriphos, oxydimenton methyl, acephat, methiocarb, thiocarb, pyrimicarb in synergic ratio.

EFFECT: agent of high efficiency to control pests and mites.

2 cl, 8 tbl, 7 ex

FIELD: organic chemistry.

SUBSTANCE: invention describes C2-phenyl-substituted cyclic ketoenols of the general formula: wherein W means hydrogen atom, alkyl with 1-6 carbon atoms; X means alkyl with 1-6 carbon atoms, alkenyl with 2-6 carbon atoms; Y means hydrogen atom, methyl, ethyl, isopropyl, alkenyl with 2-6 carbon atoms, ethynyl; Z means hydrogen atom, alkyl with 1-6 carbon atoms under condition that at least one of residues W, X, Y or Z means a chain with at least 2 carbon atoms but only one of residues X and Y can mean alkenyl with 2-6 carbon atoms; CKE means one of the following groups: , , and wherein A means hydrogen atom, alkyl with 1-6 carbon atoms; B means hydrogen atom, alkyl with 1-6 carbon atoms; A and B in common with carbon atom to which they are bound mean cycloalkyl with 5-6 carbon atoms wherein the ring carbon atom can be substituted with oxygen atom and can be substituted with alkyl with 1-6 carbon atoms or alkoxyl with 1-6 carbon atoms; A and B in common mean group of the formula: D means hydrogen atom or phenyl substituted with fluorine atom if CKE means group of the formula (4); G means hydrogen atom (a) or one of groups of the formula: or wherein R1 means alkyl with 1-6 carbon atoms, alkoxymethyl with 1-2 carbon atoms; R2 means alkyl with 1-4 carbon atoms; A and Q1 in common mean alkanediyl with 3-4 carbon atoms; Q2 means hydrogen atom. Invention provides preparing compound of the formula (I) possessing with insecticide, acaricide and herbicide activity.

EFFECT: valuable properties of compounds.

2 cl, 8 tbl, 32 ex

FIELD: agriculture, fungicides.

SUBSTANCE: claimed composition contains two components as active ingredients in synergistically effective amount in combination with respective filler, wherein component 1 represents O-methyloxime of 2-[α-{[(α-methyl-3-fluoromethylbenzyl)imino]oxy7}ortho-tolyl]-glyoxylic acid methyl aster, and component II represents compound selected from group containing II1 4-(2,2-difluoro-1,3-(benzodioxol-4-yl)-pyrrol-3-carbonitrile (fludioxanyl); II2 4-(2,3-dichlorophenyl)-pyrrol-3-carbonitrile (phenpiclonyl); II3 1-methylcyclohexanecarboxylic acid (2,2-dichloro-4-hydroxyphenyl)-amide (phenhexamide); II4 2-{2-[6-(2-cyanophenoxy)-pyrimidine-4-yloxy]phenyl}-3-methoxyacrilic acid methyl ester (azoxystrobin); II5 methoxyimino-(2-ortho-tolyloxymethylphenyl)-acetic acid methyl ester (cresoxymemethyl). Method for controlling and preventing of plant diseases also is disclosed. Claimed method includes application of stricken plant parts with component I and component II on any order or simultaneously in synergistically effective amount.

EFFECT: fungicide of high activity.

3 cl, 6 tbl, 4 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: organic chemistry, insecticides.

SUBSTANCE: invention describes an insecticide agent comprising synergetic mixture of compound of the formula (I): wherein W, X, Z, R and G have values given in the invention claim and one of the following compounds: lufenuron, triflumuron, novaluron, fluphenoxuron, emamectin, methoxyphenozide, endosulfan, fipronil, ciromazin, indoxacarb. Insecticide activity of the proposed agent is higher as compared with sum of activities of individual active substances.

EFFECT: enhanced activity of agent.

2 cl, 23 tbl, 6 ex

FIELD: organic chemistry.

SUBSTANCE: claimed method includes reduction of 2-nitro-3-phenyl-Δ5-norcamphene with active hydrogen obtaining by reaction of aluminum containing in nickel-aluminum alloy with potassium hydroxide, wherein 1 N potassium hydroxide solution and powdered nickel-aluminum alloy are added to 2-nitro-3-phenyl-Δ5-norcamphene solution in tetrahydrofurane followed by treatment thereof with ethanol in presence of skeletal nickel catalyst forming in reduction step to produce N-3-phenyl-2-norcamphanyl)-N-etnylamine followed interaction thereof with hydrogen chloride and isolation of target product. Compound of present invention is useful in medicine as active ingredient of preparations with tonic action.

EFFECT: new method for production of N-(3-phenyl-2-norcamphanyl)-N-etnylamine hydrochloride.

1 cl, 1 ex

FIELD: chemistry.

SUBSTANCE: in adamantane amino-derivatives of general formula (1), R=OH, R1=R2=R3=H, R4=C2H5, X=Cl, n=1 (I); R=Br, R1=R2=R3=H, R4=C2H5, X=Br, n=1 (II); R=OH, R1=R2=H, R3+R4=-CH2CH2CH2CH2-, X=Cl, n=1 (III); R=Br, R1=R2=H, R3+R4=-CH2CH2CH2CH2-, X=Br, n=1 (IV); R=OH, R1=R2=CH3, R3=R4=H, X=CI, n=1 (V); R=CH3, R1=-CH2OH, R2=R3=R4=H, X=Cl, n=1 (VI).

EFFECT: higher antiviral activity of derivatives towards influenza virus.

1 cl, 1 tbl, 9 ex

FIELD: biotechnology.

SUBSTANCE: invention relates to new symmetrical diimines based on camphor of general formula 1a-f, which are inhibitors of influenza virus reproduction (strain A/California/07/09 (H1N1) pdm09). In the general formula 1a-f The compounds along with pronounced antiviral activity against the said influenza virus have low toxicity.

EFFECT: chemotherapeutic index exceeds that of the known reference preparations three or more times.

1 tbl, 8 ex

FIELD: medicine, pharmaceutics.

SUBSTANCE: present invention refers to new compounds of formula I or their pharmaceutically acceptable salts possessing the properties of a neuronal nicotinic receptor antagonist. The compounds can find application for treating a disease or condition, which represents irritable bowel syndrome with diarrhoea (IBS-D), overactive bladder (OAB), nicotine addiction, smoking cessation, depression, major depressive disorder, or hypertension mediated by neuronal nicotinic receptor activity. In formula I: each of R1 and R2 individually represents H, C1-6alkyl, or R1 and R2 are bound to a nitrogen atom to which they are attached, to form 3-8-merous ring; R3 represents H, C1-6alkyl; each of R4, R5, R6 and R7 individually represents H, C1-6alkyl; L1 represents a linker specified in a group consisting of CR8R9, CR8R9CR10R11 and O; L2 represents a linker specified in a group consisting of CH2, CH2CH2, CH2CH2CH2 or CH2CH2CH2CH2; each of R8, R9, R10 and R11 individually represents hydrogen or C1-6alkyl, and a dashed line represents an optional double bond.

EFFECT: producing salts possessing the properties of the neuronal nicotinic receptor antagonist.

15 cl, 1 tbl, 9 ex

FIELD: chemistry, pharmaceutics.

SUBSTANCE: described is application of sulfonic acids and their derivatives of formula (I) and pharmaceutically acceptable salts of said compounds (see radical values in invention formula) for obtaining medication for inhibition of human PMN chemotaxis, induced by IL-8 and sulfonic acids and their derivatives of formula (I). Described are three methods of obtaining of the said compounds and pharmaceutical composition based on them.

EFFECT: compounds of formula (I) possess inhibiting activity of human PMN chemotaxis.

11 cl, 2 tbl, 6 ex

FIELD: chemistry.

SUBSTANCE: present invention pertains to new cycloalkylidene compounds with formula (I), to their pharmaceutical salts, esters and amide, capable of selective bonding ERα- and ERβ-estrogen receptors, as well as to pharmaceutical compositions based on them, their use in making medicinal preparations and the method of selective bonding ERα- and ERβ-estrogen receptors. . Denotations of R1-R7, X, p, q, as well as specific representatives of new cycloalkylidene compounds are given in the formula of invention.

EFFECT: obtaining new cylcoalkylidene compounds.

31 cl, 6 dwg, 108 ex

FIELD: chemistry.

SUBSTANCE: invention relates phenyl pyrrole derivatives formula (I) where: A denotes =NOR4, O; R4 denotes, C1-C6 alkyl; R1 denotes C1-C6 alkyl, C1-C6 alkoxy, halogen-C1-C6 alkyl, halogen-C1-C6 alkoxy, NH2, mono- C1-C6 alkylamino, halogen-mono-C1-C6 alkylamino, di(C1-C6 alkyl)amino, halogen-di-(C1-C6 alkyl)amino; or A and R1 together with the carbon atom with which they are bonded form a 5- or 6-member heterocyclic aromatic group or a heterocyclic group with partially or completely reduced saturation, which can be benzo-condensed, can contain 1-3 heteroatoms selected from N, O and S, which can be substituted and contain 1 or 2 α substitutes; R2 denotes phenyl which can be substituted with 1 or 2 α substitutes, or a 6-member heteroaryl group containing 1 or 2 N atoms, which can be substituted with 1 or 2 α substitutes; R3 denotes OH, C1-C6 alkoxy, values of α are given in claim 1, or a pharmaceutically acceptable salt thereof.

EFFECT: compounds exhibit glucokinase activating activity, which enables use thereof in treating diabetes.

51 cl, 1 tbl, 132 ex

FIELD: medicine, pharmaceutics.

SUBSTANCE: invention refers to a compound presented by formula (E) , wherein X, Y and L are independently non-directionally specified in -C(R1)(R2)-, -C(R3)=, -N(R4)-, -N= and -O-; M and Z are independently non-directionally specified in ; ---- means an optional double bond; R1, R2, R3, R4 and R6 are independently specified in hydrogen; C1-4 alkyl; group -C1-4 alkylene-halogen; group -C1-4 alkylene-OH; Hal is specified in F, Cl, Br and I; RE1 and RE2 are attached to neighbouring carbon atoms, and RE1 and RE2 together non-directionally form the structure -T-(CRE7RE8)n-V-, wherein T is specified in CRE9RE10 and O or NH, and V is specified in CRE9RE10 and O or NH, as well as respective structures comprising a double bond; at least one of T or V represents O or N; RE7 and RE8 represent H or F; RE9 and RE10 represent H; n takes on the values of 1 to 2; RE3 represents C1-6 alkyl group; m takes on the values of 0 or 1; RE4 represents a halogen atom; p takes on the values of 0 or 1; as well as to pharmaceutical diagnostic compositions of the above compound.

EFFECT: preparing the new pharmaceutical compounds.

41 cl, 17 dwg, 2 tbl, 17 ex

FIELD: medicine, pharmaceutics.

SUBSTANCE: invention relates to compounds of formula , where R1 represents L1C(O)OT; R2 represents C1-C10alkyl; n is equal 0; R4 and R5 independently represent H; L1 represents bond; T represents ethyl, propyl, isobutyl, n-butyl; and its pharmaceutically acceptable salts, stereoisomeric mixtures and enanthiomers.

EFFECT: compounds provide anaesthetic action in mammals.

8 cl, 8 dwg, 7 ex

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