SU1148564A3 - Method of obtaining derivatives of arylphenyl ethers or their acid-additive salts or their metallic complex - Google Patents

Abstract

The method of obtaining derivatives of arylphenyl ethers of the general formula APO, where Y is -CH or -N; RX and R. is a hydrogen or halogen atom or C —C alkyl, AG is unsubstituted or once or bi-; multiply substituted by halogen atom: C — C-alkyl, meth-. hydroxy group, nitro group and / or methyl trifluoride phenyl or naphthyl and V C-Cd-alkyl or form one of the following alkylene bridges: ng Кз R4 - (tijiu where Rj and R is a hydrogen atom, C - alkyl or rpynna-CH20R | ( where RJ is a hydrogen atom, C-C3 alkyl, C-C alkoxy group is substituted methyl and is substituted by a halo atom or alkyl, phenyl; CO Rj R and. R is atOM hydrogen or C-C alksh1, the total number of atoms carbon should not exceed 6, or their acid additive salts, or their metal complexes, about t l and h aa yi and so that the compound foria mules — €) cf We didn’t have a Wu, or where 4 Me is a hydrogen or alkali metal atom, condense with a compound of the formula AG-0 where AG, R RJ, and V have the indicated values;

Description

X is a halogen atom, in the form or in the form of an acid additive

at 20-220 0 in a polar inert salt medium, or in the form of a metallic complex organic solvent and high base-interaction with an equimodel of the target product in a free-flowing amount of metallic salt.

1148564

The invention relates to a process for the preparation of simple derivatives of arylphenyl ethers of the formula where Y is -CHi or: -N; R and R is a hydrogen atom or a halo gene or alkyl; . Ar is unsubstituted or singly or twice protected by a halogen atom with C-e-alkyl. Methoxy group, nitro group and / or methyl methyl phenyl or naphthyl and V-C-C-alkyl or form one of the following alkyl, new bridges ng Of 4 where R and S. is a hydrogen atom, C-C-alkyl or a group -CHgORg (where Rg is a hydrogen atom, C-Cd-alkyl, substituted C-C-alkoxygroup is substituted methyl and substituted by a halogen atom or C-Cj-alkyl phenyl ); R and R, a hydrogen atom or C -C-alkyl, and the total number of carbon atoms should not exceed 6, or their acid addition salts, or their metal complexes. These compounds can be used to combat phytopathogenic & fungi, as antimycotic and / or antioxidant and anticonvulsant active principles, to treat parasitic fungi in warm-blooded animals and / or to treat various types of epilepsy, anxiety, stress, and fungi adeny and / or manic shower disorders, as well as microbicides for plant protection, Kzvestea method based on the condensation reaction of an alkyl or aryl halide with an alkyl or aryllithium or other gim metal schelochnm l J. object of the invention - preparation of compounds of formula (I), having valuable biological activity & w properties. The goal is achieved in that according to the method a compound of the formula -CH or. a hydrogen atom or an alkali metal, fused with a compound of the formula -0 QF-V R, Rg, U and V have the indicated values -, halogen atom. 31 with ZO-ZZO C in a polar inert organic solvent and the desired product is isolated in free form or as an acid addition salt, or as a metal complex by reacting the base with an equimolar amount of the metal salt. S, N-dimethylformamide, N, N-dimethy, p-thetamide and methyl sulfoxide, acetonitrile, benzonitrile, and others are used as the polar inert solvent. Solvents of this type can be used together with other inert solvents under the conditions of this reaction, such as aliphatic or aromatic hydrocarbons, for example benzene, toluene, xylene, hexane, petroleum ether, chlorobenzene, nitrobenzene and others. Example t. Preparation of 2- (p (phenoxy) -phenyl -2-1- (1H-1,2,4-triazolyl) -methyl} -4-methyl-1,3-dioxane (6.8). Production of 2- (p - {phenoxy) -phenyl -2-bromomethyl-4-methyl-1, 3-dioxane. 10 parts of 2- (p- {phenoxy) -phenyl} -2-hydroxy-1-bromomethane and 4 hours 1.3 -butanediol is heated to 40 kp absolute toluene in the presence of 0.2 h, a catalytically active p-toluenesulfonic acid is heated under reflux for 3 h. The water is separated by means of a water separator. After cooling to room temperature, the reaction mixture is washed twice with 20 ml water, dried with sodium sulfate, filtered, solvent the crude product is evaporated and recrystallized from isopropanol. Colorless crystals are obtained with a mp of 96-106 ° C. Obtaining the desired product: 3.3 parts t, 2,4-triazole sodium salt and a catalytically active amount of potassium iodide is stirred in 40 ml dimethyl sulfoxide together with 10.2 parts of the resulting 2- (p-phenoxy) -phenyl) -phenyl 2-bromomethyl-4-metsh1-1, -dioxane for 30 hours with the mass of the reaction medium. After cooling to room temperature, 300 ml of water are added, the mixture is extracted three times with 30 ml of ethyl acetate, the combined extracts are washed twice with 20 ml of water, dried with sodium sulfate, filtered and the solvent is evaporated. The oily residue is purified by column chromatography (silica gel, ztilate) for 64L. After evaporation of the solvent, the oily residue is crystallized by the addition of petroleum ether. Brown crystals are obtained with so pl. 99.5-10GS. Example 2. Preparation of 2- {p- (4-chloro-2-methylphenoxy) -phenyl -2-Cl-imidazolylmethyl) -4-methoxymethyl-1, 3-dioxolane (3.226). 16 parts of (4-chloro-2-methylphenoxy -) - phenyl -2- (1-imidazolylmethyl) -4-hydroxymethyl-1,3-dioxolane are dissolved in 150 ml of M, H-dimethylformamide, while passing a stream of nitrogen. and mixed with stirring, 1.9 h. 55% dispersion of sodium hydride and heating for 2 hours before. After cooling to room temperature, 6.3 parts of methyl iodide is added dropwise with stirring over 1 hour, the reaction mixture is heated to 60 ° C for 2 hours, diluted with 800 ml of ice-water and extracted three times with 300 ml of ethyl acetate. The combined extracts are washed twice with 50 ml of water, dried with sodium sulfate, filtered and the solvent evaporated. The residue is purified by column chromatography (silica gel – ethyl acetate 1: 1). After evaporation of the solvent mixture, the diastereomeric mixture is crystallized by treating with hexane. Beige crystals are obtained. 92-106 ° C. Example 3. Preparation of 2-Gp- (2-nitro-4-trifluoromethyl, phenoxy) -phenyl -2- (1-imidazolylmethyl) -4-ethyl-1, 3-dioxolane (3.263). 8.3 parts of 2- (p-hydroxyphenyl) -2- (1-imidazolylmethyl) -4-ethyl-1, 3-dioxolane are dissolved in 300 ml of dimethyl sulfoxide and mixed with 1.84 parts of powdered potassium hydroxide, and the temperature rises from 23 to. After heating for 2 hours, 7.4 hours, 4-chloro-3-nitrobenzotrifluoride in 100 ml of dimethyl sulfoxide, are added dropwise with stirring (at) and stirred for 3 hours at. After cooling to room temperature, the reaction mixture of BMniraaioT in 2000 ml of water and dalzdy extracted with 200 ml of diethyl ether. Vol, uniform extracts washed twice with 70 mp water | dried with sodium sulfate and evaporated solvent. The oily residue is purified by column chromatography (silica gel - ethyl acetate. After evaporation of the solvent, the diastereomer mixture is obtained in the form of a pulp) Example 4. Synthesis of 2- (p- (3-chlorophenoxy) phenyl} -2- (1- imidazolyl -methyl) -4-ethyl-1,3-dioxolane (3.12) 1.2 parts of the sodium salt of imidazole and catalytically acting iodide were added in 50 ml of dimethylformamide together with 4. parts of (3-chlorophenoxy) phenyl - 2-bromomethyl-4-ethyl-1, 3 diaxolan for .17 hours in the mass of the reaction mixture. After cooling, the brown reaction mixture 150 ml of water are extracted three times, 50 ml of et 1-shaacet are extracted three times, the combined extracts are washed twice with VEET 50 ml of water, dried with sodium sulfate, filtered and the solvent is evaporated. The oily crude product is chromatographed on a 35-cm silica gel, using a mixture of acetone and ethyl acetate (1: 1). After evaporation of the solvent, the oily residue is crystallized by the addition of petroleum ether to give slightly yellow crystals. from m.p. 69-71 C. Example 5. Preparation of (4-chlorophenoxy) -phenylZ-2- (1-imidazol-1-w-methy-1) -4-atyl-153-dioxolane. Preparation of (4-chlorophenoxy) -phenyl -2-metsh-1-4-ethyl-1,3-dioxolane 37 parts of 4- (p-chlorophenoxy) acetophenoia and 18 parts of 1,2-butanediol are heated to 400 MP absolute toluene in prisu. 2 hours of catalytically active toluenesulphonic acid for 14. hours with the water separator switched on with an extra fridge. After cooling to room temperature, the reaction mixture was washed two times with 400 ml of water, dried with sodium sulfate. The solvent was evaporated to purify the product, which was crude in purity, and chromatographed on a 1 m column of silica with a mixture of ligroin and hexane, ethyl acetate and toluene (5 : 3: 1: 1). Get the product in the form of a slightly yellowish oil., P 1,5527. Preparation of p- (4-chlorophenyloxy) -phenyl -2-bromomethyl-4-ethyl-1, 3-dioxolane. 36.8 parts of (4-chlorophenoxy) -phenyl -2-methyl-4-ethyl-1, The 3-dioxolane is heated to 350 ml of chloroform until boiling. When illuminated with a 150 W Spot lamp, 19.4 hours of bromine dissolved in 50 ml of chloroform is added dropwise, then heated for 2 hours under reflux. After cooling to stone temperature, the reaction mixture is washed twice with 200 ml of water, dried with sodium sulfate, filtered and the solvent is evaporated in a vacuum created by a water jet pump. To purify the crude product in terms of its purity, it is chromatographed on a 1 m long column filled with silica gel with toluene. Get the product as a yellow oil, p. | 1.5805. Synthesis of the target product. 4.4 parts of sodium imidazole salt and catalytically active potassium iodide in 80 ml of dimethylformamide together with 14.7 parts of (4-chlorofensh1) -phenyl -2-bromomethyl-4-ethyl-1, 3-dioxolane are stirred for 17 hours at a bath temperature of 125 ° C. After cooling to room temperature, the reaction mixture is poured into 600 ml of water, extracted three times with 200 ml of ethyl acetate, the combined organic phases are washed twice with 200 ml of water, dried with sodium sulfate, filtered off and the solvent is evaporated. The oily residue is chromatographed on a 50 cm long column with silica gel with a mixture of acetone and ethyl acetate (1: 1). After evaporation of the solvent, the product is obtained as a brown oil, n | f 1.5750. . Example 6. Synthesis of (phenoxy) -phenyl -2- (1H-1,2,2,4-trnazolylmethyl) -4-ethyl-1,3-dioxolane (1.9). .17 h (phenoxy) -phenylZ-8-. β-bromomethyl-4-ethnl-1,3-dioxolane, 8.4 h, potassium carbonate, 4.2 h; -1,2,4-triazole and catalytically acting sodium iodide are stirred in 100 ml of dimethyl sulfoxide for 24 h with temperature within the reaction mixture 125C. After cooling to room temperature, the reaction mixture is poured into 600 ml of 11 water, extracted three times with 200 ml of ethyl acetate, the combined extracts are washed twice with 200 ml of water, dried with sodium sulfate, filtered and the solvent is evaporated. The oily residue is chromatographed on a 50 cm long column of silica gel with a mixture of chloroform and ether (1: 1). After evaporation of the solvent, the residue is crystallized by the addition of petroleum ether. Get white crystals with so pl. 61.5-83 ,. Example 7. Synthesis of (phenoxy) -phenyl -2- (1H-1,2,4-triazole1methyl) -1,3-dioxane (6.1). 14 p.2 - p-phenoxyphenyl -2-bromomethyl-1, 3-dioxane, 7.2 parts of potassium carbonate, 3.6 p.1,2,4-triazole and catalytic potassium iodide are mixed in 100 ml dimethyl sulfoxide for 2 hours at a temperature in the preliminaries of the reaction mixture 140 ° C. After cooling to room temperature, 600 ml of water are added, and 200 MP ether are combined, extracted three times. the extracts are washed twice with 200 ml of water, dried with sodium sulfate, filtered and the solvent is evaporated. The oily residue is chromatographed on a 50 cm long column of silica with a mixture of chloroform and ether (1: 1). After evaporation of the solvent, the residue is crystallized, containing petroleum ether (mp. 129-130 ° C). gg00 about g /, Example 8. Synthesis of (phenoxy) -fensch13-2- (1H-1,2,4-triazoliumI methyl) -4-oxymethyl-1,3-dioxolane (t.23). 4,5 (p-phenoxyphenyl) -2-bromomethyl-4-hydroxymethyl-1, 3-dioxolane, 2.2 parts of potassium carbonate, 1.1 parts of 1,2,4-triazole and the catalytically active potassium iodide is stirred in 50 ml dimethyl sulfoxide for 4 hours at a very high temperature. After cooling to room temperature, 600 ml of water are added, the mixture is extracted twice with 200 ml of ethyl acetate, the combined extracts are washed twice with 200 ml of water, dried with sodium sulfate, filtered and the solvent is evaporated. The oily residue is chromatographed on a 50 cm long column with silica gel with acetone. After evaporation of the solvent, the oily residue is crystallized by adding petroleum (mp. 111-122 ° C. Example 9. Synthesis of 2-p-phenoxy) -phenyl -2- (1H-1,2,4-triazolylmethyl) -2-p- propyl-1,3-dioxolane (1.17). 10.3 parts of 1- (p-phenoxyphenyl-2- (1,2,4-triaolyl) ethanol nitrate, 6.1 h, 1,2-pentanediol, 6.9 h of p-toluene sulfonic acid, 20 h, 1-pentanol and 200 parts of xylene are heated for 6 days with a drainage system and reflux condenser and, after cooling to room temperature, are washed twice with 200 ml of dilute sodium hydroxide solution and twice with 200 ml of water. The organic phase is dried with sodium sulfate, filtered and the solvent is evaporated. the residue is chromatographed on a 1 m column of silica gel with ethyl acetate. After evaporation of the oil solvent the precipitate slowly crystallizes. Beige crystals are obtained with a melting point of 68.5-71 ° C. Example 10. Preparation of 2 - {(2-methy-1-4 -phenoxy) -phenyl3-2- (1-imidazolylmethyl) -4- ethyl-1,3-dioxolane (5.73). Preparation of 2-methyl-4-phenoxyphenacyl bromide. To 36.6 parts of 2-methyl 1-4 phenoxyacetophenone, 25.9 hours of bromine in 160 ml of acetic acid are added dropwise with 1.5 hours. After the addition is complete, stir for 1 hour at room temperature, then drink 1 liter of ice water and extract twice with 100 ml of ether. The combined organic extracts are washed well with water, dried over sodium sulfate, filtered, the solvent is evaporated and the crude product is extracted with hexane. Get brown crystals with t.gsh. B-BT C. Preparation of 2- (2-methyl-4-phenoxy) -phenyl -2-bromomethyl-4-ethyl-1, 3-dioxolane. 85.4 hours of 2-methyl-4-phenoxyphenazhbromide and 25.2 hours of 1,2-butanediol are heated in 250 mp of absolute toluop in the presence of 1 hour of catalytically active p-toluenesulfonic acid for 24 hours with a water separator and reflux condenser. After chill. After stirring to room temperature, the reaction mixture is washed three times with 250 ml of water, dried with sodium sulfate, filtered and the solvent is quenched. Creeping product in the form of reddish oil. N Synthesis of the target product. 9.5 hours of the resulting 2- (2-methyl-4-phenoxy) -phenyl -2-bromomethyl-4-ethyl-1, 3-dioxolane, 2.4 parts of imidazole and 4.0 hours, of potassium tert-butylate are stirred in for 30 h in 50 ml of dimetip sulfoxide at an internal temperature POS. After cooling to room temperature, 300 m of water are added, three times extracted with 150 ml of ethyl acetate, the combined extracts are washed with water to neutrality, dried with sodium sulfate, the solvent is evaporated, and the oily residue is chromatographed on a 50 cm column of ethyl acetate . The product is obtained in the form of a reddish oil, nj) 1.5550. Example 11. Getting A. - and diastereomers (1.24 and 1.25) (phenoxy) -phenyl -2- (1H-1,2,4-triazolylmethyl) -4- (p-chloro) -benzyloxymethyl-1, 3-dioxolane. To 14.1 parts of (phenoxy) phenyl -2- (1H-1,2,4-triazolmethyl) -: 4-oxI methyl-1,3-dioxolane in 100 ml of absolute dioxane is added dropwise with stirring and passing nitrogen at room temperature, the 1.8 55% dispersion of sodium hydride in 100 ml of absolute dioxia is heated for 3 hours until. After cooling to room temperature, 8.6 parts of p-chlorobenzyl bromide are added under stirring for 30 minutes in 50 hours of absolute dioxane, the reaction mixture is heated to 50 ° C for 3 hours, then cooled to room temperature and added 1200 ml of ice-water and three times Extracted with 200 ml of ethyl acetate. The combined extracts are washed twice with 70 ml of water, dried with sulphate, filtered, and the solvent evaporated. The remaining diastereomeric mixture is separated by column chromatography (silica gel). iloc After evaporation of ethylag tata diaste, the rheomer B becomes hard (mp. 83-85 ° C). The diastereomer A remains barely drying in high vacuum as a viscous, light brown salt, Pr1,5865. Example 12. Preparation of 2 (phenoxy) -phenyl1-2- l- (1-1,2,4-triazolyl) methyl -1,3-dioxolane (1.1). 11 parts of (phenoxycarbones1) phenylJ-2- tl (1H-1,2,4-triazolyl) methyl -1, 3-dioxolane are heated in 200 ml of simple ethylene glycol diethyl ether (approximately 10 hours) until the formation of dioxide carbon. The solvent is then distilled off under reduced pressure. After cooling to room temperature, the oily crude product is dissolved in 500 ml of diethyl ether, procreated twice with 100 MP of water, dried with sodium sulfate, filtered and the solvent is evaporated. The remaining crystals are purified by recrystallization from ethyl acetate-cyclohexane in the presence of activated carbon. Get white crystals with so pl. 110-102 C. Similarly receive the final products (unless otherwise indicated) in the form of diastereomeric mixtures with different dosages of the mixture (Table 1). Example 13. Preparation of 2 (4-chlorophenoxy) -2-methylfens13-2-1- (1H-1,2,4-triazoylmethyl) -4-ethylZ-1, 3-dioxolane. 30 parts of (4-chlorophenoxy) -2-netilfen1sh -2-bromomethyl-4-ethyl-1, 3-dioxolane, 13.3 parts of the sodium salt of 1,2,4 triazole and 1 h, sodium iodide is stirred for 24 hours in 200 ml of triamcd hexamethiphosphoric acid at internal temperature. After cooling to room temperature, the mixture is poured onto 600 ml of water and extracted three times with ethyl acetate in 300 ml portions. The combined organic extracts are washed with water until neutral, dried with sodium sulfate, filtered, the solvent is evaporated, the oily residue is chromatographed on a column of silica gel 50 cm long with ethyl acetate. Poluchm-product in the form of a brown resin, p 1, 57 18. Example 14. Preparation of 2- p- (4-chlorophenoxy) -2-methylphenyl3-2-l- (1H-1,2,4-triazolylmeth1) -4-methyl J-1,3-dioxolane. 51.4 (4-chlorophenoxy) -2-methylphensh1 -2-bromomethyl-4-methyl-1, 3-dioxolane, 24.2 hours of sodium salt of 1,2,4-triazole and 0.8 parts of iodide

sodium is mixed in 150 ml of sulfolane for 5 hours at 220 ° C. The reaction mixture is then cooled to room temperature, drunk in 300 ml of water and extracted three times with 250 ml of ethyl acetate. The combined extracts are washed twice with water, 200 ml each time, dried with sodium sulfate, filtered, and the solvent is distilled off under reduced pressure. The oily residue is purified by column chromatography (silica gel-ethyl acetate).

After evaporation of the eluent, a mixture of diastereomers is obtained in the form of a low mass, p 1.5600.

Example 15. Preparation of 2 (4-trifluoromethylphenoxy) -phenyl J-2-l- (1H-l, 2,4-tripiazolylmethyl) -4-ethyl-1, 3-dioxolane.

7.4 h, sodium salt of 1,2,4-triazole and catalytically acting potassium iodide are stirred in 150 ml of dimethyl sulfoxide together with 27 h (4-trifluoromethylphenoxy) -phenyl -2-bromomethyl-4-ethyl-1, 3-dioxolane at internal cooling for 36 hours. After cooling, the brown reaction mixture is extracted into 800 ml of water, extracted three times with 200 ml ethyl acetate, the combined extracts are washed twice with 500 ml water, dried with sodium sulfate, filtered, and the solvent is evaporated. The oily raw material is chromatographed on a column of silica gel 70 cm in length. Chloroform and ether (1: 1)

After the eluent is suspended, the product crystallizes as white crystals from T.Sh1. 106-107С.

Example 16: Preparation of (4-chlorophenoxy) -2-chlorophenyl-2-l- (1H-1,2,4-triazolylmethyl) -4-ethyl-1, 3-dioxolane.

5.4 p. (4-chlorophenoxy) -2-chlorofensh1} -2-bromomethl-4-ersh1-1, dioxolane, 2.3 hours. Sodium t salt, 2 4 -triazole and catalytically acting sodium iodide for 12 h stirred in 20 ml of triamide hexamethylphosphoric acid at an internal temperature of 160 ° C. After cooling to room temperature, the mixture is poured onto 150 ml of water and extracted three times with 30 ml of ethyl acetate. The combined organic extracts are washed with B1odo until neutral, dried with sodium sulfate, filtered, and the solvent

An oily residue is chromatographed on a silica gel column 20 cm long with ethyl acetate.

The product is obtained in the form of a yellowish highly viscous oil, p 1.5773.

Example 17. Preparation of (4-chlorophenoxy) -phenyl -2-ClClH-t, 2, -triazolylmethyl) -4-MeT TJ-1, .3-dioxolane.

8.5 parts of sodium salt of 1,2,4-triazole, 1 part of potassium iodide and 18 hours (4-chlorophenoxy) -phenyl3-2-bromo-methyl-4-methyl-1, 3-dioxolane are stirred for 3 days in 80 ml of triamide hexamethylforsoric acid at an internal temperature of 50 ° C. Then the brown reaction mixture is poured onto 500 ml of water and extracted three times with 200 ml of ether. The organic extracts are washed twice with 200 ml of water each time, dried with sodium sulfate, a tat filter, the solvent is evaporated, the oil is chromatographed on a silica gel column with a length of 35 cm, chloroform, and ether (1: 1) for purification.

After evaporation of the eluent, an oily residue crystallizes (by adding petroleum ether) as yellow crystals with mp. 8184 ° C.

Example 18. Preparation of (4-chlorophenoxy) -phenylZ-2-1- (| Н-1, 2,4-tripiazolylmetsh I) -4,5 dimethyl-1,3-dioxolane.

3j6 h, sodium salt of t, 2,4-triazole and catalytically active yo.disty potassium are stirred for 10 days in 30 ml of triamide hexamethylphosphoric acid together with 8 h. (4-chlorophenoxyphenyl) -2-bromo-methyl-4, 5-dimethyl-1,3-dioxolane at 20 ° C. Then the brown reaction mixture is extracted three times with 100 ml of ethyl acetate. The combined extracts are washed twice with 100 ml each of water, dried with sodium sulfate, filtered, and the solvent is evaporated. The oily residue is crystallized as ether to obtain yellow ether (mp. 95-97 °.

Example 19. Preparation of (4-bpo rheoxy) -2-chlorophenyl 3-2-1- (1H-1,2,4-triazole 1-m-1) -4-myal-1, 3-dioxolane.

15.6 hr. (4-bromophenoxy) -2-chlorophenes I)} - 2-bromomethyl-4-methyl-1,3-dioxolane, 6.2 hr. Sodium salt

152,4-triazole and 0.3 h, sodium iodide is stirred for 16 h in 40 ml of 1-methyl-2-pyrrolidone at an internal temperature of 150 ° C. After cooling to room temperature b, the reaction mixture is diluted with 250 ml. water and twice extracted with ethyl acetate 200 ml. The combined organic extracts are washed with water until neutral, dried with sodium sulphate, fresh, dissolved and evaporated. The oily residue is purified on a chromatographic column (silica gel-ethyl acetate Ji. After evaporation of the eluant, the mixture of diastero-eomar is obtained as a viscous mass, 5B97,

Example 20 Preparation of - (4-chlorophenoxy) -2-chlorophenyl-2-fl- (1H-1, 2,4-triazolylmethyl) -4-20-methyl -1,3-dioxane.

15 parts (4 chlorophenoxy) -2-chlorophenyl;} - 2-bromo-4-methyl-t, 3-dioxane, 6.4 parts of 1,2,4-triazole sodium salt, catalytically acting sodium iodide for 7 hours stirred in 50 ml of sulfolane at 200 ° C. Then the reaction mixture is cooled to room temperature, poured onto 200 MP of water and extracted three times with 70 ml of ethyl acetate. The extracts are washed with water until neutral, dried with sodium sulfate, filtered, and the solvent is evaporated. The oily residue is chromatographed 35 on a 25 cm long column of silica gel with ethyl acetate.

After evaporation of the eluent, the product is obtained in white crystals (mp, 104-106 C) .40

Example 21. Obtaining - (4-bromophenoxy) -fensch1} -2 t- (1H-1, 2,4-triazolylmetsh1) -4-n u opilj-1, 3-dioxolane.

6.5 hours of sodium salt of 1,2,4 triazole, 1 part of potassium iodide and 25 hours of (4-bromophenoxy) -phenyl 3-2-bromomethyl-4-n-propyl-1, 3-dioxolane 60 hours, stirred in 150 mp dimethyl sulfoxide at an internal temperature of 90 GiSO. After cooling to room temperature, the reaction mixture is poured onto 800 ml of water and extracted three times with 250 ml of ethyl acetate. The combined organic phases are washed twice to 200 ml, dried with sodium sulfate, the solvent is evaporated. An oily residue for the purification of chromatographic

Fyre on a column of silica gel with the use of chloroform and ether in a 1: 1 ratio. After volatilization of the solvent, the oily residue is recrystallized by means of petroleum ether.

Yellow crystals are obtained. 81-83c.

Example 22. Obtaining (4-chlorophenoxy) -PhenylJ-2-Li- (1H-1, 2,4-triazolylmethyl) -4-methyl} -1,3-dioxane.

11.9 hours (4-chlorophenoxy) -phenyl-2-bromomethyl-4-methyl-1, 3-dioxane,

3.1 h sodium salt of 1,2,4-triazole,

6.2 parts of potassium carbonate and 0.5 parts of potassium iodide are stirred for 85 hours in 50 ml of dimethyl sulfoxide at internal temperature. After cooling to room temperature, the brown reaction mixture is poured onto 300 ml of water and extracted three times with 100 ml of ether. The extracts are washed twice with 100 ml of water, dried with sodium sulfate, filtered, and the solvent is evaporated. The oily residue is chromatographed.

on a 40 cm long column of silica gel using methylene chloride and ether in a 1: 1 ratio,

After solvent extraction, a mixture of diastereomers is obtained in the form of a viscous mass, p 1.5748,

Example 23. Obtaining (D-bromophenoxy) -2-methylphenyl -2 -1- (1H-1,2,4 triazoliumImidSHI) -4-sItylZ-1, 3-dioxolac,

13.9 h, (4-bromophenoxy) -2 - -methylphenyl -2-bromomethyl-4-ethyl-. -1,3-dioxolane, 5,3 parts of sodium salt of 1, 2,4-triazole and 0.2 parts of sodium iodide are stirred for 12 hours in 30 parts of 1-methyl-2-pyrrolidone at 155 ° G. After cooling to room temperature, 200 MP of water are added to the reaction mixture and extracted three times with 100 ml ethyl acetate. The soy extracts are washed with water until neutral reaction, dried with sodium sulfate, filtered, and the solvent is evaporated. For the purpose of purification, the oily residue is chromatographed on a column of silica gel ethyl acetate. Get the product in the form of a yellow resin, nj) t, 577

Example 24, Supplementation of (4-chlorophenoxy) -2-hporpenyl -2-t- (1H-1,2,4-triazolylmethyl) -4-n-propyl -1,3-dioxolane.

3.7 parts (4-chlorophenoxy) -2-chlorophenyl) -2-bromomethyl-4-n-propyl-1, 3-dioxolane, 1.5 h, sodium salt 1,2,4-triazole and 0 1 hour. Sodium hydroxide is stirred for 25 hours in 25 ml of hexamethylphosphoric acid triamide. After cooling to room temperature, the reaction mixture is poured onto 100 ml of water and extracted twice with 40 ml of ethyl acetate. The extracts are washed with water.

until neutral, dried with sodium sulfate, F1 <1>, the solvent is evaporated. The oily residue is purified by silica gel column chromatography with ethyl acetate.

The compound is obtained as a yellow resin,, 5707.

In tab. 1-10 shows the characteristics of the compounds and their isomeric forms (Symbol A means diastereomer type A, B diastereomer type B,

Table 1

H

N

N

n

H

CH

CHj

N

CHj

N

sn,

N sn,

CH SN

N

3

,

N

N

N

N

with a

N

C, H5

CH

CH

С2%

CH

N

100-102

HNO,

85-92

NS g

sisg.

MnCNOj)

81.5-83.5

HNOj ZnCl.

MnCNO FeCE,

Light brown oil

CuC,

68,5-7t

17

CHgOCHgHQH Cl N

t.24

CH20CH2- - € 1 N

1.25 CH20- / -CHN N 1.26

18

1148564

Continued table. one

Viscous p2pCH oil, 5865 (A)

83-85 (B) 107-109 (A)

90-94 (B)

1 / 2CuSO.

Continued table. 2

21

2.31

, 2.32 2.33 ff. 2.34

mon 2.35

sn. 2.36

sn. 2. 37

(.38

- (snr2 .39

- (snrts, 2.40 - (.41 - (sn) 2 .42 - (snd2.43 - (.44

 Oil, p | s 1,5643

15

CHj

N N N N CHZ

all CjHj

cf

Cjhs

22:

1148564

continuation of the table. 2

HCI

N N N

Mn (NOj) j, (COOH) (COOH),

ch i

N

i

NGZO

N

w sn

HNQj

N N N N N

(NOj)

(Coo} g

ZnCEt

not ZncEj,

us

Table 3

74-76

N N CH

SNS

N N N N CHj

HNG

se

Cucl ce

N) H (n) H GgH.d) H CjH, (i) H) H H CH, () g () 2 () 2 3.27 H (),

HCt (COOH), 1.5750 5-cN 111.5-114 5-cEN N Mn (NOJ nN - 96-98 n: cn 69-71 nNnNnnn nN5-cN 5-cN HNHNO HNNN HN N Oil, pd 1, 6086

Continued table. 3

Continued table. 3

 85-90

29

thirty

1148564 Continued table. 3 311148564 32 Continuation of the table. 3

Continued table. 3

Continued. 3

37114856438

Continued table. 3

one

OCHj

H H Cl

CHjOCHj

OCHg

CHjOCH

H H H H H H H H H H CHjOCH CSCH

CH, NO

N0

C, Hj

N0 C, H,

Cl

Cl

CHjiOCHj

Cl

SNGOSN

NO,

SN, SNOS

NOj

,

NOj

H

H

H

H

H

H

,

H

NOj

C, Hy

H

N0

CH

NOj

H

Shagnz

H CHjOCHj

CFj, H.

H

CHiOCHj

H

CTjpCH,

H CjHj

NO

CF,

CHjOCH, H CH OCgHs

H H

from 2115

CH OCItj

Continued table. 3

zz;

-ten

,

6-ClCH

6-cln

HCH

HCH

HCH

HN

HCH

HCH

Hk

HCH

HCH

HN

106-107

HN

HCH

HN

96-102 HCH

HN

HN

HCH

75-78

5-CH ,, CH

5-CHj CH S-CHj N 5-CH, CH

N

H H

N

S-CHj CH

CHj

64-73 5-CHj N CH 5-CH, CH CH,

Continuation of table

45 114856446

Continued table. 3 471148564. 48 Continuation, table. 3

49 1148564 50

, - to ... Continuation of the table. 3

51

 1148564

52

Continued table. 3

.k D - V

Yu C

55 4.32Н () 2Н H 4.33Н () 2 CHj H 4.34Н () 2 H 24 .35Н () 2 H 4.36Н (() 2, HH 4.37Н H () 2H 4.38Н. In () 2 H 4.39 H () 2 H 4.40Н Cl (CH «· H) j H .4.41СН, Cl () 2H 4.42Н Cl (CH« CH) 2 H 4.43Н С, Н, Ч CH,) 2H 4.44Н CHj (CH -CHijH 4.45I Cl () 2 34 .46I CHj () 2 44 .47H CH, (), H 4.48CHj CHj HHH 4.49CHj CHj H OWh H 4.50W. HH (KShz H 4.51CjH -n H CHj HH 4.52CjH , -n H CHj H 0 € Hj a 4.53 CdH5 H CHj H OCHj H 4.54HCH OCHj FHHH 4.55HGj Hj FHHH 4.56HCH OCHs HFHH 4.57HCjHj HHFH 4.58HC HS HFHH

56J

1148564

Continued table. 4 f HHNN CR N CH NN 2-ClH 3-ClH HH HH H. H 3-N02 H 3 - N02H flH 2-Cl.H 2-ClH 3-ClH HH 2-Cl6-Cl 2-ClH HH 2- Cl H 2-CH5 H Ti4note-resin 2-CH5 H 2-CH3 H Sheaf nt, 5628 2-CHsH 2-CHjH 2-CH, H 2-ClH 2-CH5H 2-ClH 2-CHjH Light brown 2-ClH resin

57 4.59Н 4.60Н CHjOCHj Cl 4.61Н CHjOCH, Cl 4.62Н 4.63Н 4.64Н 4.65Н 4.66Н H Cl H 4.67Н J Br HHHHH 4.68Н FHH 4.69Н HHF 4.70Н CHjOCH, Br HH 4.71Н сНгОСН, Br HH 4.72Н CHjpCHj H Br H 4.73H H Br H CjH, 4.74H CHjOCHj 4.75H 4.76H CH, HH 4.77H 0% HH 4.78H H CHjH 4.79H CH3 CHjOCHj 4.80H CHj HH CH 4.81H CHjOCHj H CHj H 4.82H CHjOCHj H HCHjH 4.83Н H 4.84Н CH, -iHH CHjOCHj 4.85Н

58

1148564 - Continuation of the table. four

CH CH CH N CH CH N CHN CH CH CH N CH N CHNN CH CH NN CH N 2 -CH, H Brown resin, 1.54 50 2-Cl 2-Cl 2-Cl 2-Cl 2- CH3 Resin, 1.5735 V 2 x (oil 2-CH3 Resin, nj 1,5493 2-Cl 2-CH3 2-CH3 Light 2-CH, brown 2411 2-Cl 2-Cl 2-Cl 2 -Cl 2 resin -Cl HKOj 105t110 2-CH3 HNOj 92-95 2-CH3 2-Cl 2-Cl HNQ. 129-134 2-CHs XA) 2-Cl 2-CH 2 2 Cl

59

60

And 48564 Continued table. four

61

HC1

N N N N

4.113CHj

N N N N

HC1

4.114 € 2%

HC1

4.115СГЩ

HC1

4.116С2%

/

N N N N N N

HF

SNE

4.117СН,

t

HF SI,

4.118GH,

HF

,

4.119 СНз

HF

Cjhs

4.120CHj

H N

HF, 4.121.N

HF 4.122 H 4.123 H

-CjH, -n Н

HF

HF H

4.124 N

HF

CHjOCH, N

4.125Н

HF CHj, OGHj H

4.126Н

HC1 N

4.127Н.

HC1

N. 4.128 Н

HC1

CHj

4.129 Н

HC1

CjHs 4.130 N

HC1

4.131Н

H

HC1

4.132Н

SI.

HC1

4.133Н

s, n, 4.134 N

HC1

SzN, -p

HC1

GHjOCBj H 4.135tt CHjН

FН 4.136 CHj

HC1

Cjhs

H N 4I37 N

4.138 N

HC1

Sa to her.

NN 4.139 N

62

P48564

Continued table. four

2-CH3

H

N N

Resin, p. 1.5600 2-OCHD

b-OCH, 2-OCHN 6-OCHD

SN 2-CH3

N N

resin 1.5718

2-CH3

H

N:

2-CH3

H

SI N

2-CH3

H

2-CH3

H

sn

2H: Ne

. N

H

2-CH3

H

sn

Resin

2-CH3

H

N

2-CH3 Resin

sn

H

2-CH3

H

N

2-CH3

H

CH

2-CH3

H

N

2-CHj

High CH

H zkoy

3-CH3

H

N butter

3-CH3

H

N

3-CH3

H

N

S-chj

H

CH

Z-CH,

CH

H

zt

H

sn sn sn

Z-SNZ

H

NSh, 131-140

2-CH5

H

N

2-SG

-Resin,

H p 1,5631

2-CH3

HNOj 124-126

CH

and

2-CH

H

N

-Resin,

63

64

1148564 Continued table. four

65

66

1148564

Continuation table

67

68

1148564 Continued table. four

Continued table. five

71 i 5.43 Cjl.-n 5.44 CjH.-n 5.45 .46 CjH.-i 5.47 2-OCH3; 48 5.49 5.51 2-OCHe 5.52 CjII, 5.53 2-OCHe 5.54 ij 5.55 2-OCHz 5.56 5.57 CjH, -1 CHjCjH, -i - (CKj) (CH,), - (SNg) -Snr - (CHj) -, -, - (CH,) - (enr, H11 СзН, -п

72 Continuation of table. five

-h 6-och 6-och 6-och 6-och (COOH) (COOH). , HNO, MnXMO,) COQH) j ZnClj HCl ZnCl, 103-106 Yellow resin n 1.5476

73P4856474

Continued Table. five

75

76.

1148564

Continued table. five.

77

ILZIIZILIOIIIZEII

one

2-CH,

Sgnu

CjH7-n 2 - CH3

2-CH a

2-CH3

GH,

, 2-chj

CH. 2-С11з

SI, 2-SNZ

C, Hj 2-CH,

CrB

1148564 Continued table. five

at

HB oil)

SN p 1.5580

N

N

73-75

TO

93-95

N

59-62

pd 1,5751

CH

HNO,

N

103-105

Hno.

SI

126-128

Table 6

"F8

79 6.29H HC, Ry-nC R 6.30H RCjR, -nCHj 6.31CH3 H HCjHjCjR 6.32HH HC H -nCRj 6.33Cl H 6-ClC R -nR 6.34Cl 6-ClCjRT-nR 6.35H RShzR 6.36F HRR 6.37H RC Rj-nR 6.38H, -nR

80

148564 Continued table. 6

ten

11 CjR, -n RR CgR CjR, -n C, R, -n CjH, -n CjHi-n CjRs 103-109 No. (Shz) N CjRi-h CR RN CRj, N 13 CH C, Hj-n N, -n CH RCR

83

84

IG48564 Continued table. yog

85

, 86.

 1148564 Continued table. 6

T a b l and c a 7

H

H

N N N N N

H N

.one

CH

.2

CH,

H

H

.3

H

CH,

CHj

H

.4 CH,

CH,

H

H

.five

CH ,,

eNz

H

CH,

.6

CHj

Ghj

CH,

to

H

.7

€ 1

6-C1

in SNZ

CH.

.8 ghj

H

Cjhs

H

H

.9 CH J

H

H

H

.ten

Cjhy

6-СНз СН,

CHj

CH

.41

H

,

s, n.

H

H

.12

c, n,

H

H

C2 "s

H

.13

H

H

H CjHs

122-124

HNOj, MnCNO,)

Oil, p 1.5782

CuCl.

(COOH) 2

HNOj

HCi

87

7. SdNu N

H H CH,

7.15CjHj CjHjf Н

7.16Н

CjHy H

7.17Н N

N N N N

7.18Н

S.gN; H

7.19НCjH -nH

7.20НCjH -nH

7.21 CH,

M onj sd-pn

7.22 N

NN

N N N N N F N N

7.23CHjSN N

7.24NNSN,

7.25ННСНз t 7.26ННН

"

7.27ННН

7.28ННН

7.29NNM

7.30and

N N N N N And

H N

H

7.31P

and

7.32Н

% N

C1 C1 C1 C1 CH,

7.33Н

N N N N

7.34Н

H

7.35Н

Shz

7.36Н

and

H

7.37Н

N N N N

H

7.38Н

H

NOj N

7.39Н

H

H

b-cp,

7.40Н

sn.

H 5-CPP

88

1148564 Continuation of table 7

Fed,

HNO,

H CuCl j

119-121

1/2 CuSO

105-107

6-C1

6-C1

5-C1 5-C1

116-118 101-103

89

RIS H CH H H H H 5-Cl H H H 2-CH 3 H H 2-CHE H Cl 6-Cl Cl H H H CH.

90

1148564.

Continued table. 7

Ri6 TV.18

RI CHj 3 CH} CHj H CHj CHj CHj H Cl H Shz CH, H H CH, H H H H H H CHj N H CHj N Mn (NO,) 2 H N

93

94

1148564 Continued table. eight

95 iIJfZriiniLE

NN

F H N N N N N N N

N F N N N N N N N N

2-СНз Н Н Н

NN

a-CH,

C1H

2-SIS

C1H

2-CH, H

C1H

2-CH N

C1H

2-CH, H

FH

2-eN-N

FH

2-CHj N

FВ 2-СНз Н

2-CH,

FH

H

8.762-СН 5

H C1 H CH3 H H N

8.772-С1 Н Н Н Вг Н Н Н Н N

96

1148564

C-

Continued table. eight

Brown

sn

N N N N N N N N. N

H resin

N N

H

H

Brown

sn

H resin

N

H

SI

H

127-137

N

H

CH

H

N

H

CH

H

п Ь5673 107-108 IIlL-IiniliL-ZiLZ

one

.J

97 9.72-С15-Ci ННС1 Нлл1 9.82-С1Н НС1С1 Н СНН СН 9.92-С1Н С1НН 6-С1 CH 9.10ЗгС15-С1 С1НН 9.112-GI6-ei ННС1 9.123-CHj5-СНзНН 9.132-СН-НННН 9.132-CHI5-СНЗНН 9.132-CHI5-СНЗНН 9.132-CHI5-СНзНН 9.132-CHI5-СНННН 9.132-CHI5-СНННН 9.132-CHI5-СНННН 9.132-CHI5-СНННН 9.132-CHI5-СНННН 9.132-CHI5-СНННН 9.132-CHI5-CHIHNH NSNzV 9.152-ei5-C1 C1NI 9.162-C1H GIC1C1 5-C1 V 9.172-C1H HC1C1 N H 6-CH3N 9.182-СЫз5-СНзННЗИН 9 о 192-СНз6-CHj HHCH H N H 9.202-I-Na-I-Nc-CH1 HNH N H 9.202 I-CH6 Nzin 9 9 192-СНЗН HHC1 HH 6-CHj No. 9.22HN C1H1 6-C1 CH2.23HH CHj HBg 9.24HH CHHHBg 6-C1 HH 9.252-C1H HNC1 9.262-C1H HHC1 9.272-C1H NIR 9.282-C1H HHF 9.292-C1HHH2NH1 9H2NHH1H2NH1H2NH1H C1H HHC1 9.312-C1H HHC1

1148564

-.

Continued table. 9 СН СНОН С, Н, Н N CuCl, Н с (€ OOH), j СНз CgHj Н Н HNO, CjHj and СНН1 CjHs Н СНРеС1з Н Н С С, H5 Н CjHff Н ННШз CjHs, Н НCuCl, CjH, -n Н CjH, -n Н CHjН CHjСзН, -n CjHj Н пд 1,5787 N. СНзН 146-154 п, Ш7 СНз п 1,5781 140-141 NHNO,

99

45 H Cl. 10. tH to .2 H H Cl. 10.3N H Sise 10.4H H CHa 5-CHj 10.5H 10.6H 10.7H 10.8N H 10.9H H 10.10iZ-Cl H HCl 10.112-C16-C1H 10.123-C1HN 10.132- С16-G1Н НС1 10.142-CHjН "10.15 2-сНз е-снд ™ з and 10.16 2-Cllj Н СНз Н 10..17 2-С1 5-С1 С1 Н Н 10.182-G1 5-С1 Н Н С1 10.192-С1 6-C1 C1 C1 C1 10.202-C1 HCCH CHi) H 10.212-CH5 H () 2 H 10.22НННН Н

100V

1148564

vTa6nHua 10

N НN НN НСН N 5-Cl N e-Cl N HN HCH HN HN HN HN HCH HN HN 6-ClN H, N 6-Cl CH HN HN CHCH ifoCNOg: CH, CH, CjHy C + Hj-n CjH , -i CH, CH3 (T.p.59-60C) CH3 (COOH), CsH, -n CzH, -n. CH CH3 CHj CHj C., HS, rn CjHif-n C s CsH, -n CH, CHj OT, CH, SenT-i CH, CH, CH, 3

103P48564104

, Continued table. .ten

1051148564106

Continued table. 10 As antimicrobial agents for plant protection, physiologically flawless inorganic and organic acids are, for example, hydrohalic acids (hydrochloric, hydrobromic, or hydroiodic, sulfuric, phosphoric, phosphorous, nitric, acetic, and oxalic acids, under certain conditions, halide hydrochloride fatty acids (trichloroacetic acid) or sulfonic acids, in particular benzenesulfonic and methanesulfonic acids. As a biologically active active principle of the drug, thus, can Useful mineral acids, for example, hydrogen halides (hydrochloric, hydrobromic and hydroiodic acid), nitrogen, sulfuric or phosphoric acid, pharmaceutically acceptable aliphatic mono- and hydroxylated dicarboxylic acids, under certain conditions, such as acetic acid, fumaric acid, for example, acetic acid, fumaric acid, for example, hydroxylated dicarboxylic acids; , Block or tartaric, and aliphatic or aromatic sulfonic acids, t, e, lower alkanoic acids or, under certain conditions, substituted benzenesulfonic acids (methane, ethane, benzene, p-toluophen and p-br mbenzene sulfonic acid and sulfamic acids, in particular C-cyclohexyl sulfamic acid. The complex compounds of formula (I) formed by metals consist of an organic molecule and an inorganic or organic metal salt, for example halides, nitrates, sulfates, phosphates, tartrates, etc. copper, manganese, iron, zinc and other metals of different valences. At room temperature, the compounds of formula (1) are stable oils, sheaf-like or solid substances that have atstivomikrobrobfshsh, for example: antifungal in plants, and pharmacological properties, especially antifungal, anti-convulsive and relieving anxiety and discomfort. In this connection, these compounds can be used, on the one hand, in agriculture to combat phytopathogenic microorganisms and, on the other hand, as antifungal and / or anti-fungal, as well as sedative biologically active substances, drugs that serve to fight against fungi that parasitize warm-blooded animals and / or to treat various forms of epilepsy, as well as conditions in which fear is felt, various stresses and agitations, and manic mental disorders Evan. By using agents in which compounds of formula (I) are used as biologically active substances, it is possible to delay the development or destroy microorganisms parasitizing plants or their parts (fruits, flowers, leaves, stems, tubers, roots) without damaging the plants. At the same time, biologically active substances are especially effective against phytopathogenic fungi belonging to the following groups: Ascomyceten (for example, Venturia, Podosphaera, Erysiphe, MohiEinia, Uncinu a); Basidioaiyceten (for example, HemiEeia, Rhizoctonia, Puccinia); Fungi imperfect (for example, Botrytis, HeCminthosporium, Fusarium, Septoria, Cercospora u Aiternaria). In addition, the compounds of formula (I) can be used as a dressing agent for treating seed (fruits, tubers, grains), as well as cuttings of plants for preventing fungal infection. The biologically active substances according to the invention are also used in antimicrobial agents,. . The effectiveness of the products based on the compounds of formula (I) was confirmed when processing grain crops (wheat, barley, rye, oats, rice, sorghum and related crops), beets (sugar and fodder beet), pods and fruits containing stones and seeds (Blonny ,, pears, plums, peaches, almonds, cherries), as well as a year (strawberry, raspberry and blackberry), legumes (beans, beans, lentils, peas, co), oil crops (rapeseed, mustard, poppy , olive, sunflower, coconut, cocoa castor, peanut), cucumber plants (pumpkin, cucumbers, melons), fiber raw plants (cotton, flax, hemp, jute), citrus fruits (oranges, lemons, pummelos, tangerines), vegetables (spinach, lettuce, asparagus, cabbage 109 different varieties, carrots, onions, tomatoes, potatoes, peppers), laurel plants (avocado, cinnamon, camphor) or various plants such as maize, tobacco, nuts, coffee, sugarcane, tea, grapes, hops, bananas, natural rubber, as well as ornamental plants (composites). The biologically active substances of formula (I) are applied to the plant surface to be treated or to a plant site simultaneously or sequentially with other biologically active substances, for example, fertilizers, intermediary agents for the introduction of trace elements or other drugs that affect plant growth, as well as selective herbicides. insecticides, fungicides, bactericides, nematode worms, molluscicides, and mixtures of several preparations with other materials customary for the formulation technique, carriers, stno-active agents or other additives. Solid or liquid carriers and additives are non-toxic substances, such as natural or regenerated materials of mineral origin, solvents, dispersants, wetting agents, preparations that contribute to the retention of the applied formulation on the treated surface thickeners or binders. Most often in agriculture the method of applying a biologically active substance of the formula (1) or an agrochemical to the diseased plant on the foliage is applied. However, the biologically active substance of formula (I) can penetrate into the plant and through the root system when applied to the soil surface (systemic effect). According to this method, the growing area is impregnated with a liquid substance or is introduced into the soil in solid form, for example in the form of a granulated pro; duct. In addition, the compounds of formula (1) may be applied to the grain by soaking it with a liquid formulation containing the biologically active substance, or testing with a powdered solid formulation. In special cases, other methods of application are possible, for example, targeted processing of plant stems or buds. Therefore, the compounds of formula 64 (I) are commercially available in the form of emulsifiable concentrates suitable for applying pastes, solutions that can be sprayed directly or requiring dilution, diluted emulsions, wettable powders, soluble powders, opioids, granulated products, and capsules in polymeric materials. The amount of application and the dose of the preparation to be applied are determined by the extent of the effect on the corresponding pathogen. Usually, from 5 mg to 50 g of active substance (AB) is used per hectare. An optimum flow rate is from 100 g to 2 kg AB / ha, preferably 200-600 g AB / ha. An agrochemical agent containing, along with the biologically active substance of the formula (e), under certain conditions, a solid or liquid auxiliary agent, is prepared by thoroughly mixing and / or grinding the active substance with an excipient, such as a solvent, a solid carrier. and under certain conditions also with a surfactant. The solvents used are aromatic hydrocarbons, preferably C – C fractions. as, for example, a mixture of xylenes or substituted naphthalenes, phthalic acid esters such as dibutyl or dioctyl phthalate, cyclohexane aliphatic hydrocarbons or paraffins, alcohols or glycols, and their esters and esters, in particular ethanol, ethylene glycol, monomethyl or ethyl simple ethylene glycol ether, ketones, such as cyclohexanone, a highly polar solvent, such as L-methyl2-pyrrolidone, dimethyl sulfoxide or dimethylformamide, and under certain circumstances: epoxidized vegetable oil, on example, coconut or soy, or water. The solid carrier is a powder from a natural mineral, such as calcite, talc, kaolin, montmorillonite or attapulgite. To improve the physical properties, finely dispersed silica or finely divided polymer can be added. The materials of a porous structure, for example, pumice, bit che111, serve as a granular absorbing carrier of granules. repic, sepiolit or bentonite. Calcite or sand, for example, serves as a carrier material without sorption properties. In addition, many pre-granulated materials of inorganic or organic origin are used, especially dolomite, as well as crushed plant residues. Nonionic, cationic and / or anionic surfactants with good emulsifying, dispersing and wetting properties, and mixtures thereof, in particular, water-soluble matter - (alkali metal, alkaline earth metal salts and unsubstituted or substituted ammonium salts of higher fatty acids (C p-CjJ, e.g. sodium or potassium salts of oily or stearic acid, or mixtures of naturally occurring fatty acids, derived from coconut or gall oil, and methyllauric salt of fatty acids), as well as water-soluble synthetic surfactants, especially fatty sulfonates, fatty sulphates, sulphonated benzymidazole derivatives or alkylarylsulphonates. Fatty sulphonates or fatty sulphates are alkali metal, alkaline earth metal salts, or unsubstituted or substituted salts, which contain alkyl A carbon with 8–22 carbon atoms, alkali and alkyl includes, for example, sodium or calcium salt of ligninsulfonic acid, dodecyl sulfuric esters or a mixture of sulfates of fatty alcohols on fatty acids of natural origin, and salts of sulfuric acid derivatives and sulfonic acids of adducts formed fatty alcohol and ethylene oxide. The sulfonated benzymidazole derivatives contain, preferably, 2 groups of hydrochloric acid and one C-atom fatty acid residue. Alkylaryl sulphonates are, for example, sodium-50thioic, calcium or triethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid or: a condensation product of naphthalenesulfonic acid with formaldehyde. Tone- 55

Corresponding phosphates are represented, for example, by salts of esters, - formed by phosphoric acid and adduct, for example, stabilizers, anti-foaming agents, viscosity regulators, binding agents. 64 that p-nonylphenol- (4-14) -oxyn ethylene. Non-non-surfactant surfactants are, first of all, derived from simple polyglycol-salt ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols, which can contain 3-30 groups of simple, glycol ether, 8-20 carbon atoms in (aliphatic a) hydrocarbon residue and 6-18 carbon atoms in the alkyl, alkyl residue of the alkylphenol, secondly, water-soluble adducts of polyethylene oxide, containing 20-250 groups of ether of ethylene glycol, and 10-100 groups of ether of propylene; stake and polypropylene in the night polyethylene glycol and octylphenoxypolyethoxyethanol, fourth; polyoxyethylene sorbitan fatty acid ester, such as polyoxyethylene sorbitol triole ata Cationic surfactants are primarily quaternary ammonium salts containing at least one alkyl residue with 8–22 carbon atoms as N-substituents, and lower-halogenated alk1-sh-, benzyl- as other e-substituents or lower oxyalkyl residue. The salts used are predominantly halides, methyl sulfates or ethyl sulfates, for example, stearyl trimethylammonium chloride or benzyl di (2-chloroethyl) ethylammonium bromide. Recipe agrochemical composition,%: AB by the formula (I) 0.1-99 (preferably 0.1-95) -, solid or liquid excipients 1-99.9 (preferably 5-99.8) including surfactant 0 -25 (especially 0.1-25). The agrochemical agent may also contain other additives for obtaining special effects, a means of maintaining the formulation on the treated surface, as well as fertilizer and other active principles. This agent is commercially available and diluted by the consumer. The antifungal properties of the compounds of formula (I) can be investigated and determined, for example, in vitro by microbiological testing using conventional methods, for example, by determining the toxic effect of the compounds on the fungus parasitizing on warm-blooded animals. animals, Trychophyton raentagryphites, Microsporum canis, Sporotrichum schenkii, AspergiEEus fumigatus u CanUida albicauSj a, also on a live organism (on guinea pigs) by acting on infected ones by ASTK of skin on the back of the fungus Trychophyton, such as T. rubrum, after oral administration or topical application. The effectiveness of the anticonvulsant action of the compounds of formula (1), and also their pharmaceutically acceptable acid addition salts, are confirmed by testing them on a living body, for example, in mice, by means of a test for the appearance of suds under the influence of pentatetrazole at a dosage of 10-tOO mg per t kg when taken by mouth or with electric shock, also at dosage tO100 mg / kg when taken by mouth. The efficacy of calming anxiety is confirmed by testing on mice and other small animals and Quatr.e Plagues (a dose of about 10 to 100 mg / kg when taken by mouth), indicating the ability of nova compounds to prevent the development of mania. . . Thus, the compounds of formula (1) and their pharmaceutical acid addition salts can be used. for the local and systemic control of fungi parasitic on warm-blooded animals, or the systemic treatment of various forms of epilepsy, states of fear and intensity, as well as mental conditions caused by mania, especially as an active ingredient in pharmaceutical preparations for enteral, parenteral local administration. The dosage of the active principle depends on the type of warm-blooded animal, its age and individual condition, as well as on the method of application. In the usual case, for a warm-blooded creature weighing about 75 kg when taken through the mouth, a safe daily dose is about 50-500 mg when divided into several identical partial doses. Pharmaceutical preparations contain, for example, about - 80% (preferably 20-60%) of active principle. The pharmaceutical preparations according to the invention for administration via the gastrointestinal tract or subcutaneously are manufactured, for example, in such single dosage forms as pills, tablets, capsules or suppositories and ampoules, by ordinary mixing, granulating, draining, dissolving or lyophilizing. Thus, pharmaceutical preparations for oral intake are obtained by combining the active principle with solid carriers, the resulting mixture is granulated, if necessary, and the mixture or granulated after the addition of auxiliary substances is processed into tablets or dragee grains. Suitable carrier materials are fillers, in particular sugar, for example lactose and sucrose, mannnt or sorbitol, a preparation of cellulose and / or calcium phosphate, for example tricalcium phosphate or disodium phosphate, a binder such as a starch processor from starch, derived from corn, wheat, rice or potatoes, gelatin, tragacanth, methylcellulose and / or polyvinylpyrrole scone, and / or agents that loosen the composition, for example, these types of starch, carboxymethyl starch, polyvinylpyrrolidone, reticular st whose structures are crosslinked together, agar, alginic acid or its salt (sodium alginate). Auxiliary agents primarily serve as a flow regulator and lubricant, for example, silicic acid, talc, stearic acid or its salts (magnesium stearate or calcium stearate and / or polyethylene glycol). Dragee grains are coated with a layer, if necessary, resistant to the action of gastric juice, and concentrated sugar solutions are used, among others, containing gumirabic, talc, polyvinylpyrrolidone, polyethylene glycol and / or titanium dioxide at certain UELA VIASES; lacquer solutions in suitable organic solvents or solvent mixtures or a solution of cellulose preparations (cellulose phthalate or hydroxypropylmethyl cellulose phthalate). Tablets or dragee coatings may contain dyes or pigments to identify them or to differentiate various doses of active ingredients. Pharmaceutical preparations suitable for ingestion through the mouth can be in the form of capsules made of gelatin and in the form of soft, closed capsules made of gelatin with the addition of a softener such as glycerin or sorbitol. Disposable capsules for ingestion through the mouth can contain the active principle in the form of a granulate, for example, in a mixture with fillers, such as lactose, a binding agent, such as starch, and / or a slip agent, as well as talc or magnesium stearate, and under certain conditions with stabilizers. In soft capsules, the active principle is preferably contained in a dissolved form and suspended in suitable liquid forms, for example, fatty oils, vasels of new oil or liquid polyethylene glycols, and stabilizers can be added. Pharmaceutical preparations used in direct kippi dp are produced in the form of suppositories consisting of an active principle in combination with the main mass, such as triglycerides of natural or synthetic origin, paraffinic hydrocarbons, polyethylene glycols and higher alkanols, for example also in the form of rectal gelatinous capsules containing the active principle in combination with the main mass, which are liquid triglycerides, polyethylene glycols or paraffin hydrocarbons. For parenteral administration, aqueous solutions of the active principle in water-soluble form are applied, for example, in the form of a water-soluble salt, suspensions of the active principle, in particular, appropriate oil suspensions for injection, and suitable lipophilic solvents or medicinal medium, solid oils, for example, sesame or synthetic fatty acid esters, such as ethyl oleate or triglycerides, as well as aqueous suspensions for injections containing substances that are viscous, for example, sodium a carboxymethylcellulose derivative, sorbitol and / or dextran, and stabilizers under certain conditions. Pharmaceutical preparations for topical administration are available in the form of creams, ointments, pastes, foams, tinctures and solutions, which include 0.5 to 20% of the active principle. Creams are oil-in-water emulsions containing more than 50% water. Fatty alcohols are used as an oily base, for example, laural, cital or stearyl; fatty acids in 4acTHOcTHj palmitic or stearic; liquid to solid socks: isopropyl myristate, wool fat (lanolin) or beeswax, and / or hydrocarbons (petrolatum (petrolatum) or petroleum jelly). Emulsifiers are surfactants with hydrophilic properties, for example, non-ionic emulsifiers: fatty acid-formed ester of polyalcohols or ethylene oxide adducts attached to them, for example, polyglycerol ester of fatty acid, ether formed by polyoxyethylene and fatty alcohol, ester, formed by full fatty acid and fatty acid; or appropriate ionic emulsifiers; fatty acid sulfate salts formed by an alkali metal, for example sodium lauryl sulfate, sodium acetyl sulfate or sodium stearyl sulfate, which are usually used in the presence of fatty alcohols, in particular, peryl alcohol or stearic alcohol. Additives to the aqueous phase are anti-drying agents, for example polyhydric alcohols - glycerin, sorbitol, propylene glycol and / or polyethylene glycol, as well as preservative agent, perfumes, etc.

Fatty ointments are anhydrous and contain, as a base, in particular, hydrocarbons, such as paraffin, petrolatum and / or liquid paraffins, as well as natural or partially synthetic fats, for example, coconut oil triglyceride, or hardened oils - hydrogenated arachia or castor oil, and in addition, partial fatty acid esters of glycerol; glycerol mono- and distearate ,, and fatty alcohols that improve susceptibility to water, emulsifiers and / or additives. . /

Pastes are creams and ointments containing powdered components that can absorb secretion products, as well as metal oxides, such as titanium oxide or zinc oxide, as well as talc and / or aluminum silicate, which bind moisture or liquid separable. Foams are thrown out of the reservoir which is under excessive pressure, and are liquid emulsions like oil in water in the form of an aerosol, and halogenated hydrocarbons, such as lower chlorofluoroalkanes, for example, dichloride, are used as an expander. methane and dichlorotetrafluoroethane. Hydrocarbons, such as liquid paraffin, fatty alcohols - cetyl ester, are the oil phase. fatty acid, isopropyl myristate and / or others, paraffin-like or wax-like substances. As emulsifiers, mixtures with predominantly hydrophilic properties are used, such as fatty acid ester, polyoxyethylene-to-1 (Tweens) ester, and also mixtures with predominant lipophilic properties,. example is ester sorbitol and fatty acid (Spans). Emulsifiers also contain conventional additives, in particular preservative agent, etc.

Tinctures and solutions in most cases contain a water-ethanol basis, to which polyalcohols are added, for example glycerol, glycols, and / or polyethylene glycol as a means of retaining moisture to reduce its loss due to evaporation and substances that compensate for the loss of fatty substances, such as ipao acid ester

with lower polyethylene glycol, i.e. with lipophilic substances soluble in aqueous mixtures, which serve as a substitute for fatty substances extracted from the skin with ethanol, as well as, if necessary, other auxiliary substances and additional agents.

Pharmaceutical preparations for topical administration are prepared, for example, by dissolving or suspending the active principle in the base material or in part thereof. In order to obtain a solution, the active principle is usually dissolved in one of the phases prior to emulsification; In order to obtain 1 and a suspension, the active principle after emulsification is mixed with a part of the base material, after which the residue for the formulation is added.

Example 25. The compositions of an agrochemical agent containing AB according to the formula (I).

Emulsion, wt.%:

The current beginning of the table. 1-10 25 40 50 Calcium dodecylbenzene sulfonate 5 86 Polyethylene glycol ether of castor oil (30 mol of ethylene oxide :) 5 - Tributylphenoyl polyethylene glycol ether (30 mol of ethylene oxide) - 124 Cyclohex non - 15 20 Mixture of xylenes 65 25 20 By dilution with water, ready t multicy of any concentration.

PRI and MER 26, Solutions, wt.%:

Active principle

potable 1-10 30 10 5 95

Monomethyl ether

ethylene glycol 20 - - polyethylene glycol; cohols (pn molecules

weight (MB) 400) - 70 - 2-Methyl-2-pyro-.

lidon- 20 - Zpoxidized coconut oil - - 1-5 Gasoline (, T.Sh1. 160190 ° C) - - 94 Solutions suitable for use in the form of tiny droplets. 119 Example 27. Granules, in the Active principle according to Tables 1-105 Kaolin.94 Finely dispersed silica 1 Attapulgite The active beginning of the solution in methylene chloride, obtained by rum, is dusting the carrier and then the solvent is evaporated in vacuo. Example 28, Detergent - weight,%: The active principle according to the table. 1-10 2 Finely dispersed silicic acid1 Talc97 Kaolin Prepared for use in cp get thoroughly 1m mixing of the carrier material with the active chal. Example 29. Wetting powder, wt.%: The active principle on the table. T-to25 50 Sodium lignin ulfonata55 Sodium lauryl sulfate Sodium dnizobutilnaftalinsulfonat 3 - 6 Oktypfenolpolietilenglikolevy ether-2 (7-8 moles of oxide: ethylene.) Finely divided silicic acid 5 tO 27 Kaolin62 active principle with careful meshivshot dopolnitelnvii vesche and peremalgaayut mill. Paul moistened with fiss powder that can be diluted with water to a slur of any concentration. Example 30. Emulsify concentrate, wt.%: The active principle on the table. t-10to Octylphenol-polyethylene glycol ether (4-5 mol of these oxides, flax) 3 Calcium dodecylbenzenesulfonate 3 Polyglycol ether of castor oil (35 mol of ethylene oxide) 4 Cyclohexanone 30 Mixture of xylenes 50 From this concentrate, dilute with water with any water. Example 31. Fermentor, wt.%: The active principle in Table. 1-10 Kaolin The active principle is mixed with an itel and milled in a mill. Example, 32. Granular arc, obtained by impalement,%: The active principle according to Table. 1-10 10 Sodium ligninsulfonate 2 Carbosimethylcellulose1 Kaolin 87 Actually, the beginning is moved by additional substances, broken and moistened with water. This mixture is worked and then dried in a stuffy stream. Example 33. Granulate, consisting of coated granules,%: Active, beginning according to Table. 1-10 3 Polyethylene glycol (MB 200) 3 Kaolin94 Finely ground evenly applied onto a mixture of kaolin on polyethylene glycol moistened with polyethylene glycol. Example 34. Concentrated, wt.%: The active principle on the table. t-iO 40 3 tylene ene glycol 10 Nonylphenyl polyethylene glycol 6 (15% ethylene oxide Sodium ligninsulfate 10 Carboxymethylcellulose 121 3 7% water solution of formaldehyde 0.2 Silicone nod in the form of 371st aqueous emulsion .Os8 Water. 32 Finely divided current extract mixed with additives. From the concentrate suspension can be diluted with water, suspensions of any concentrate Example 35. Preparation of pharmaceutical preparations. Composition (A-Chlorshenoxy) -phenyl -2- (1 1-shidazolylmethyl) 4-e-tyldiohssolan5, 0 Vaseline 45.0 Paraffin oil 19, 6. Tons of alcohol 5,0 W. bees 3.0 I Sorbitol sesquioleate 5.0 Ester of p-hydroxybenzoic acid 0.2 Water is demineralized Up to 100.0 Fatty substances and emulgate are fused together, the preservative is dissolved in water and p is introduced into the melted pit at elevated temperatures with by cooling the emulsion. After cooling, the pension is kneaded with one part of the fat melt in the emulsion. Example 36. Creams, weight 2-p-Oslorphenoxy) -: -phenylL-2- (1-imidazolylmethyl) -4-ethyl- -1.3- dioxolane 10.0 Isopropyl palmitate 8.0 Zet1-eshpalmitat U 5 Silicone oil 1000.5 Sorbitol monostearate 3.0 Polysorbate 60-3.5 1.2 Pops ngly- col-PH; 20.0 Acrylic acid polymerization 0.5 Triethanolamine Demineralized water - Up to 100.0 Acrylic acid polymerization product is suspended in a mixture of purified water with T, 2-propyl glycerol. Then, triethanolamine is added with mixing, in a cut of 64 which results in mucus. A mixture of isoproshshpalmitat, tsetnalpalmitat, silicone oil, sorbitan monostearate and polysorbate is heated to 75 ° C and the slime heated to 75 ° C is mixed while stirring. Cooled to room temperature, the base cream is then applied to make a concentrate with a valid start. The concentrate is homogenized using a flow-through homogenizer, after which it is added to the base portions. Cream, wt.%; (Chlorophenoxy) -phenylZ-2- (1-imidazolylmethyl) -4-ethyl--1, 3-dioxolane 5.0 Cetyl palmitate PH 2.0 Cetyl alcohol PH 2.0 A mixture of trglycerides saturated. 5.0 Fatty Acids of Average Fat Stearic Acid 3.0 Glycerin Stearate PH 4.0 Cetomacrogol-1000 1.0 Microcrystalline Cellulose 0.5 1.2 Propyl 1 Glycol Distilled 20.0 Water Demineralized Up to 100.0 Cetyl Alcohol, Cetyl Palmitate, Blend triglycerides, stearyic acid and glycerol stearate are fused. Microcrystalline cellulose is dispersed in a portion of the Water. Cetomacrogol and propylene glycol are dissolved in the residual part of the water, mucus is added with stirring. The fatty phase is then added with stirring to the aqueous phase and the mixture is further stirred in the cold. Then the active principle is ground with a part of the base and the ground mass is kneaded into the remaining amount of cream. Example 37. Hydrogel (clear), wt.% 1 2-fn-Chlorophenoxy) -phenyl J-2- (1-imidazolylmethyl) -4-ETSh1dnsolena5 Propylene glycol 10-20 Isopropano 20 Oxypropylmethylcellulose. 2 Water Up to 100 Oxypropylmethylcellulose is allowed to swell in water. The active ingredient is dissolved in a mixture of isopropanol and propylene glycol. Then, the solution of the active substance is mixed with our cellulose derivative and additionally smelled with an arsenicizing additive (O, 1%). Example 38. Foaming aerosols, w / l: (Chlorphenoxy) -phenyl3-2- (1-imidazolylmethyl) -4-ethyl-1, 3-dioxolane 1.00 Cetyl alcohol PH 1.70 Paraffin oil thick 1.00 From opropyl myristate 2.00 Tsetamakrogol sorbitan monostearate 2.40 1.50 1,2-Propsh1englikol pH5-00 0.18 Methylparaben 0.02 Propilpareben Hemodern-314 0.10 Water demineralized to 100 Cetyl alcohol, paraffin ma isopropyl myristate, sorbitan stearate and cetomacrogol Melted Methylpropylparaben dissolved in hot water. Then the melt and solution are perforated. The active principle is suspended in proppylene glycol, kneaded into the base. A chemoder and water are then added to the final weight amount. Aluminum vessels for single dosage, supplied in til, are filled with a mixture (20 MP each) and an aerosol-forming gas (under pressure). Example39. Capsules are desirable. Composition for tOOO capsules, g: (Fenbksi) -phenyl} -2- l- (1H-t, 2,4-triazolyl) -methyl g1, 3-dioxane 200 Lactose of the hammer 100 The active substance and lactose (t tea grinding) mix . The resulting powder is sieved and portions (0.20 g each) fill the yellow capsules. Example 40. Tablets. Composition of 1000 tablets, each containing 25 mg of the active substance, g: 424 (Phenoxy) -phenyl -2-1- (1H-1,2,4-triazolyl) -methyl -1, 3-dioxane Lactose Wheat starch Polyethylene glycol 6000 Magnesium stearate Water is demineral to saturation. All solid constituents are first ground through a sieve with a hole size of 0.6 mm. Then the active substance, lactose, t.alkol, magnesium stearate and half the amount of starch are mixed. The other half of the starch is suspended in 40 ml of water and the resulting suspension is added to the boiling solution of polyethylene glycol in 100 ml of water and the mixture is granulated, if necessary, with the addition of water. The granulate is dried overnight, rubbed through a 1.2 mm sieve and pressed into tablets with a diameter of about 6 mm with two-sided stretching. Tablets, each containing 100 mg of active ingredient each (1000 tablets), g: (Phenoxy) -phenyl -2- {1- (1H-1,2,4-triazolyl) -methyl -1,3-dioxane Lactose Wheat starch Polytilled glycol -6000 Talc Magnesium Stearate Demineralized water Water HacMaevana None All solid constituents are first wiped through a sieve with cells with a diameter of 0.6 mm. The active substance is then mixed in with lactose, talc, magnesium stearate and half the amount of starch. The other half of the starch is suspended in 40 ml of water, and this suspension is added to a boiling solution of polyethylene glycol in 100 ml of water, and the mixture is granulated with the addition of water. The granulate is dried at 85 ° C. overnight, rubbed through a sieve with cells 1j2 mm wide and pressed into tablets with a diameter of about 6 mm with double-sided concavity. Tablets containing 75 mg of active napa each (1000 tablets), g: 2-fn- (phenoxy) phenl -2 1- (1H-1,2,4-triaolol) -methyl -153 Dioxane Lactose Wheat starch Polyethylene gly- / col-6000 magnesium stearate. water is demineralized until saturation. All solid constituents are first rubbed through a sieve with cells with a width of 0.6 t-iM. The active substance, lactose, talc, magnesium stearate and half the amount of starch are then kneaded. The other half of the starch is suspended in 40 ml of water and the resulting suspension is added to the boiling solution of polyethylene glycol in 100 ml of water and the mixture is granulated after the addition of water. The granulate is dried overnight at 35 ° C, rubbed through a 1.2 mm wide sieve and compressed into tablets of about 6 mm in diameter with double-sided strength. Similarly, pharmaceutical preparations containing other active substances listed above can be prepared. in tab. Example 41, Effect on Figinia graminis on wheat. Residual-protective action. Wheat plants 6 days after sowing were sprayed with a working solution (l4, 25 and 50%) wettable powder (diluted with water) as in example; 29 containing 0.06% AB according to the table 1-10. After 24 hours, the treated plants were infected with a fungus uredospore suspension. After incubation for 48 hours at 95–100% of relative air humidity and approximately infected plants, they were exposed in a greenhouse at approximately 22 ° C. The development of rust fungus pustules was assessed through. 12 days after infection. System action To wheat plants after 5 days. after sowing, a working aqueous solution (25, 50 and 75%) was poured in a solution of a wettable powder according to Example 29, containing 0.006% of the active substance according to tab. 1-10 (based on the volume of soil). After 48 h, the treated rats were infected with a fungus uredospore suspension. After incubation for 48 hours at 95-100% relative humidity and approximately infected plants were exposed in a greenhouse at approximately 22 ° C. The development of rust fungus pustules was assessed 12 days after infection. The compounds according to Table. 1-10 showed a good action against Puccinia rust fungi. Untreated infected control plants were 100% affected by rust fungi. The results are shown in Table. 11. .T. a b l and c a 1 Remaining-protective action (defeat,%)

127 Continued table. eleven

128

1148564 About the relation table. P

In addition, compound 6.8 in these preparations showed a gingole suppression of rust fungi of the genus

-4 o

About About 2 1

856430

Puccinia at a consumed dose of 0.006%, Compound No. 6.8 was tested as a granulate according to Example 27. Tests showed a good systemic effect of this compound against the rust fungi of the genus Puccinia (0% damage).

Example 42. Action against CercQspora arachidicoEa on peanut plants.

Hazelnut plants with a height of 10–15 cm were sprayed with a working (25% solution of a wettable powder, in Example 29 containing 0.02% of the active substance according to Tables 1–10. Water 5 (40 and 50% emulsion of the example. 25) and an aqueous 95% solution according to Example 26. After 48 hours, the test plants were infected with a suspension of conidia of fungi.Infected plants were incubated for 72 hours at approximately 21 ° C and high humidity and exposed to greenhouse until the appearance of typical spots on the leaves The fungicidal action was evaluated 12 days after infection on again the number and size of the formed pen ..

Compared to untreated infected control plants (the number and size of the spots are 100%), the peanut plants treated with AB according to the table. 1-10, had significantly less damage from Cercospora.

The results are shown in Table. 12. Table 12

3

about 1

ABOUT

oh oh

about

133

Defeat,% when treated with goods

Contents, for example, 29 40% 25%

134

1148564

The continuation of the table 12 according to example 25 g-nm150Zh-nym according to example 26 of the 95% Example 43. Action against Erysiphae graminis on barley. . Residual-protective action. Plants of barley with a height of about 8 s were sprayed with a working 25 and 75% solution of a wettable powder according to example 29 containing O, X) 2% of the active substance according to the table. 1-10 and Hbw water (80% and 5% solution of Example 26. After 3-A h, the treated plants were pollinated with conidia of fungi. Infected plants were placed on the face approximately and the lesions with fungi were evaluated after 10 days. Systemic action. Barley plants about 8 cm high were watered with a worker (50% solution of a wettable powder, co0-4

3.6

1.1

3.7

1.9

1.14

3.8

thirty

Continued tabl, 12

3.133

3.155

ABOUT

3.156

About holding 0,006% active ingredient in the table. 1-10 (based on the volume of soil). At the same time, they paid attention to the fact that the solution did not fall on the parts of plants that were found above the soil surface. After 48 hours, the treated plants were pollinated with conidia of fungi. Infected plants were placed in a greenhouse at approximately 22 ° C and fungal damage was assessed after 10 days. The compounds of formula (l) showed a good residual protective and systemic action against fungi Erysiphae. The results are shown in Table. 13. Untreated infected control plants had a 100% lesion from fungi. Table 13

137

Oh oh

3.11 3.12 3.26

0-5 О О 3.51 3.52

0-3 3.54 0-4 3.55 О О 3.127

4-5

4.23 10 5-8

4.50

4.57 About

4.59

0-3

4.66 4-5

4.70 5

.4.77

3-5

4.78 8

4.81

0-4

4.89 0-2

4.90 O 11

4.91

4.92

.5-7

4.93 5-8

4.94 O O 10

4.113

4.116

4.136

138

1148564

Continued table. 13

ABOUT .

3.162

0-2 0-4

3.164

About 2-5

3.168

ABOUT . 0 0-3

3.171

2-5

3.172

0-3 0-3

3.176

5-6

about

3.177

0-3

0-5

3.193

ABOUT

3.212

0-5

5.40

2-3

About About About About

5.70

2-5

5.71

ABOUT

5.73

ABOUT

2-5

5.75

About 3-6

5.76

About About About About About About

5.77

3-6

5.78

ABOUT

6.1

ABOUT

6.8

ABOUT

6.17

ABOUT

6.79

0-3

LTD

6.80

5-8

7.3

ABOUT

7.7

ABOUT

3-5

7.21

0-2 2-3

7.33

ABOUT

, t About

7.34

4-5

139

Compounds 3.164, 4.50 and 6.8 exhibited a systemic effect (0% lesion) at concentrations up to 0.006%.

Example 44. Residual-protective action against Venturia inaeguatis.

Blon's cuttings with young shoots .BpteHoft TO-20 cm were sprayed with a work (t (75% -H№i). a solution of a wettable powder, according to Example 29, containing 0.06% of the compound according to Table. 1-10 and

Example 45. Action against Botrytis cinerea on beans.

Residual protective action.

Bean plants about 10 cm high were sprayed with a worker (25, 50, and 75% wetted solution

140

11A8564 Continued table. 13

aqueous solution (95 and 10% solution according to example 26. After 24 hours, the treated plants were infected with conidia of fungi. The plants were then incubated for 5 days at 90-100% relative humidity of air and placed for the next 10 days in a greenhouse at 20 -24 ° C. String damage was assessed 15 days after infection. The results are shown in Table 14.

Untreated infected shoots showed in all experiments 100% damage from Venturia. .

, Table 14

powder according to example 29, containing 0.02% AB according to the table. 1-10 and an aqueous (40%) emulsion of Example 25. After 48 hours, the treated plants were infected with a suspension of conidia of fungi. After an incubation period of infected plants for 3 days at

143

144 Table 16

1148564

Continued table. sixteen

Claims (1)

The method of obtaining derivatives ’SIMPLE ARILPHENYL ETHERS or their ACID-ADDITIVE SALTS, or their METAL COMPLEXES. (57) Method for the preparation of derivatives of simple arylphenyl ethers of the general formula te tf Ж \ Σ / 9 ^- θ / = ^ Ν X where Y is —CH = or —Ν =; R, and - a hydrogen or halogen atom or C ₇ -C ₃ ~ alkyl ·, Ag - unsubstituted or single or double; multiple substituted by a halogen atom, C, -C ^ -alkyl, meth-. oxy group, nitro group and / or methyl trifluoride phenyl or naphthyl; U and V - with, -C ₃ -alkyl or form one of the following alkylene bridges: r ₄ :) - <UJ7U where R ₃ and R ₄ are a hydrogen atom, C, - C ₊ - alkyl or a group-CH ₂ OR _g (where R _& is a hydrogen atom, C, -C3-alkyl, by means of C, -C ^ -alkoxygroup substituted methyl and substituted by a halogen atom or C, -C ₃ alkyl (phenyl); Atom of hydrogen or C ^ -C ^ apkyl, and the total number of carbon atoms should not exceed 6, or their acid additive salts, their metal complexes of the mule and mule R ₅ R _$ and. R _? or, on the basis of the fact that the connection form -CH- or -N-; • where Y Me is an atom of hydrogen or an alkali metal, they are condensed with a compound of the formula where Ar-0 i Ar, R ₇ , R _t , U values; and v have specified msHi ^yu ns X is a halogen atom at 20-220 ° C in a polar inert organic solvent and the target product is isolated in free form or as an acid addition salt, or as a metal complex by reaction of the base with an equimolar amount of metal salt.