Condensed heterocyclic derivatives, methods for their preparation, composition based on them, a way of combating fungi

 

(57) Abstract:

The invention offers a condensed heterocyclic compound represented by formula

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where R is a lower alkyl group, Alchemilla group, etc.; R2, R3, R4, R5, R6independently are a hydrogen atom, lower alkyl, etc.,; W represents a fragment-OC(O)-, -SC(O)- and so on; Z is 2-indolines group, etc. In the invention it is also proposed agricultural or horticultural fungicide which contains condensed derivative, which is an effective fungicide. Agricultural or horticultural fungicide according to the invention exhibits a high ability to control the impact of Phytophthora and downy mildew without harming negribkovoy photosynthetic plants. 5 S. and 11 C.p. f-crystals, 14 PL.

The invention relates to derivatives of heterocyclic compounds, as well as agricultural and horticultural fungicides containing these compounds as active ingredients. The invention also relates to a method of obtaining derivatives of condensed heterocyclic compounds.

So far, it was known that certain derivatives of the Xia, for example, N-(tert-butoxycarbonyl)-L-valine-4-methoxyphenylacetamide [2] N2-phenoxycarbonyl-N1-[raceme-1-(4-chlorophenyl)ethyl]-L-isoleucine [3] N-isopropyl-oxycarbonyl)-L-valine-4-methoxyphenylacetamide (see Japanese patent application 4-230652), N2-phenoxycarbonyl-N1-[raceme-1-(4-chlorophenyl)-ethyl] -L-cyclopentylamine (Japanese patent application 4-230653), N2-Deut-butyloxycarbonyl-N1-[S(+)-1-cyclohexylethyl]-L-valinamide (see Japanese patent application N 4-283554), benzyl (D,L)-1-[3,4-dimethoxyphenethyl)carbamoyl] -n-butyl} carbamate [3] N-(ISO-propylenecarbonate)-L-valine-diphenylmethylene (see Japanese patent application N 4-338372), etc.

These compounds, however, are not sufficiently effective to be used as pesticides. Moreover, previously known documents do not describe the derivatives of amides of amino acids, containing condensed heterocyclic ring, such as, benzopyrrole ring, benzothiophene ring, etc. For this reason, the usefulness of derivatives of amides of amino acids was unknown.

The aim of the invention is the provision of a new condensed heterocyclic derivative exhibiting excellent Integra and has conducted extensive research on its influence on the physiological activity of fungi. In the end, they found that the compounds according to the invention exhibit antifungal activity against a wide range of mold and plant diseases and at the same time demonstrate a high security against negribkovoy photosynthetic plants.

In accordance with the first aspect of the invention features a condensed heterocyclic derivative represented by the formula

< / BR>
where R1lower alkyl group, which optionally contains at least one Deputy, selected from the group comprising halogen atom, cyano and methoxy group, Alchemilla group, Alchemilla group, cycloalkyl group which may contain at least one methyl group, cycloalkyl group which may contain at least one methyl group, cyclic ether group which may contain at least one methyl group, arylalkyl group which may contain at least one Deputy, selected from the group comprising methyl group, methoxy group and a nitro group, phenyl group which may contain at least one Deputy, selected from the group comprising an atom of Galaga carbonilla group;

R2, R3, R4, R5and R6independently represent a hydrogen atom, a lower alkyl group which may contain at least one halogen atom, cycloalkyl group or arylalkyl group, phenyl group, cyano group, acyl group, lower alkoxy group or lower alkoxycarbonyl group;

R2can form with R3cycloalkyl ring containing 3-6 carbon atoms.

represents a fragment represented by the following formulas

< / BR>
where X is a hydrogen atom, a halogen atom, an alkyl group which may contain at least one halogen atom, Alchemilla group, methoxy group, triptoreline group, hydroxyl group, methoxycarbonyl group, methylcarbazole group, amino group, dimethylamino group, a nitro group, a methylthio group, methylsulfinyl group, methylsulfonyl group, phenyl group, acetyl group, formyl group, or cyano group;

n is an integer 1, 2 or 3;

A represents O, S, N or fragment

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where R7is a hydrogen atom, methyl group, acetyl group or benzoline group;

W represents-C(O)-, -N proposed agricultural or horticultural fungicide, containing condensed heterocyclic derivative as an active ingredient.

In this description, the term "lower" used in the sense of "containing not more than 6 carbon atoms". The term "alkyl group" means an alkyl group with straight or branched chain, containing 1-15 carbon atoms, and includes, including groups such as methyl group, ethyl group, n-sawn group, ISO-sawn group, n-bucilina group, ISO-bucilina group, sec-bucilina group, tert-bucilina group, n-pencilina group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 2,2-dimethylpropylene group, 1,1-dimethylpropylene group, 1-ethylpropyl group, n-exilda group, n-heptylene group, n-aktiline group, n-nanlina group, n-decile group, n-angellina group, n-Godzilla group, n-redecilla group, n-tetradecyl group, n-pentadactyla group, etc.

Lower alkyl group, which optionally contains at least one Deputy, selected from the group comprising halogen atom, cyano and methoxy group may be, for example, monochloroethylene group, trichlorethylene group, 1-cyanoethylene what uppoi etc.

The term "halogen" means fluorine atom, chlorine atom, bromine atom, iodine atom, etc.,

The term "Alchemilla group" is used to denote alkenylphenol group with a straight or branched chain containing 2 to 6 carbon atoms, and includes, including groups such as vinyl group, 1-protanilla group, 2-protanilla group, ISO-protanilla group, 2-bucinellina group, 3-bucinellina group, 1-methyl-1-protanilla group, 2-methylpropenyl group, 1-ethylenimine group, 2-penttila group, 2-exilda group, etc.

The term "Alchemilla group" is used to denote alkenylphenol group with a straight or branched chain containing 2 to 6 carbon atoms, and includes, for example, ethyl group, propenyloxy group, butenyloxy group, 1-methyl-1-propenyloxy group, 2-pentelow group, 2-hexylamino group, etc.

The term "cycloalkenyl group" is used here to denote cycloalkyl group containing 3-8 carbon atoms, and includes, in particular, cyclopropyl group, cyclobutyl group, cyclopentyl group, tsiklogeksilnogo group, cycloheptyl group, cyclooctyl group, etc.

Cycloalkyl groppello group, 2-methylcyclopropyl group, 1-methylcyclobutene group, 2-methylcyclobutane group, 1,2-dimethylcyclobutyl group, 1-methylcyclopentanol group, 2-methylcyclopentanol group, 3-methylcyclopentadienyl group, 1,2-dimethylcyclopentene group, 1,2,3-trimethylcyclopentanone group, etc.

The term "cycloalkenyl" is used to denote cycloalkenyl group containing 3-8 carbon atoms, and includes, including groups such as 1-cyclopropylamino group, 2-cyclopropylamino group, 1-cyclobutenyl group, 2-cyclobutenyl group, 1-cyclopentenyl group, 2-cyclopentenyl group, 3-cyclopentenyl group, 1-cyclohexenyl group, 2-cyclohexenyl group, 3-cyclohexenyl group, 1-cycloheptenyl group, 2-cycloheptenyl group, 3-cycloheptenyl group, 2-cyclooctadiene group, 3-cyclooctadiene group, 4-cyclooctadiene group, etc.

Next, cycloalkenyl group which may contain at least one methyl group, includes, for example, 1-methyl-2-cyclopentyloxy group, 2-methyl-1-cyclopentyl group, 3-methyl-1-cyclopentenyl group, 3,4-dimethyl-1-cyclopentenyl group, 1-methyl-2-cyclohexylidene group, which probably contains at least one Deputy, selected from the group comprising methyl group, methoxy group and a nitro group can be, for example, 4-methylbenzyl group-methylbenzyl group, 4-methoxybenzyl group, 4-nitrobenzyloxy group, 2,4-dimethylbenzyl group, 2-methyl-3-methoxy-4-nitroaniline band-methyl-4-methylphenylethyl group, etc.

The term "cyclic ether group" is used here to denote a cyclic ether group containing 2-6 carbon atoms and includes, for example, a group of oxirane, group 2-oxetane, group 3-tetrahydrofuro, group 2-tetrahydropyrane, etc. Acyl group include acetyl group, benzoyloxy group, etc.

Cyclic ether group which may contain at least one methyl group can be, for example, 2-methoxyaniline group, 2-methyl-3-tetrahydrofurane group, 1,4-dimethyl-3-tetrahydrofuryl group, 2,4,5-trimethyl-3-tetrahydrofuryl group, etc.

Phenyl group which may contain at least one Deputy, selected from the group comprising halogen atom, methyl group, methoxy group, nitro group and methoxycarbonyl the th, 4-nitroaniline group, 4-metastrongylidae group, 2-methoxy-4-nitroaniline group, performanceline group, etc.

Preferred compounds according to the invention are compounds represented by formula I, where R1an alkyl group with straight or branched chain containing 2 to 6 carbon atoms, Allenova group with a straight or branched chain containing 3 carbon atoms, cycloalkyl group containing 5-6 carbon atoms, or unsubstituted phenyl group; R2a hydrogen atom; R3ISO-sawn group; R4a hydrogen atom, phenyl group, methyl group or ethyl group; R5is a hydrogen atom or a methyl group; R6a hydrogen atom; W represents-OC(O)-; Z is substituted heterocyclic group, including benzofuranyl group, benzothiophene group, indole group, 2,3-dihydrobenzofuranyl group, which contain one or two (same or different) substituent such as a hydrogen atom, fluorine atom, chlorine atom, nitro group, cyano group or methyl group; the amino acid is an L-isomer.

Compounds according to the invention, represented by formula I can exist when there are one or two hirlarious, enantiomers and their mixtures that can be separated using appropriate methods.

Finally, the compounds according to the invention, represented by formula I, are given in table. 1-7. It should however be noted that the invention is not limited to these compounds. The compounds listed in the table. 1-7 will be described below.

In table. 1-7 compounds 1, 2 and 3; compounds 68, 69 and 303, the connection 70, 71 and 296; connection 129, 130 and 131; connection 136, 137, and 138; connection 108, and 109 375; connection 382, 23 and 24, the connection 376, 163 and 164; connection 377, 378 and 379 are a mixture of diastereomers, as well as are individual diastereomers. Further, compounds 16 and 17; compounds 97 and 98; compound 102 and 103; 115 connection and 327; connection 132 and 133; connection 227 and 362; connection 228 and 364; connection 230, 365; connections 223 and 363; connection 336 and 337; connection 405 and 406; connection 423 and 424 are a mixture of diastereomers, and are, respectively, one of the individual diastereomers. Connections 161 and 162 are individual diastereomers.

Compounds according to the invention, represented by formula I, can be obtained as follows.

The method of obtaining AND

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where R1, R2, R3, R4, Rwhat armoloy I, can be obtained by the interaction of the derived amino acid, represented by formula II, or a derivative of the amino acid with the activated carboxyl group with an amine represented by the formula III in the presence of a base and/or catalyst, if necessary.

In this reaction as the derived amino acid represented by the formula II with an activated carboxyl group can be, for example, galoyanized acid such as the acid chloride, etc., an acid anhydride derived from two molecules derived amino acids represented by formula II, a mixed anhydride derived from the derived amino acid, represented by formula II, and the other acid and/or 0-alkalicarbonate acid, activated ester, 2-peredelnyj ether, etc., These compounds can be obtained by conventional methods (see, for example, Methods der Organischen Chemie, Vol. 15, No,2, p.2; Georg Thieme Verlag Stuttgart: 1974; Chemische Berichte, 1905, Vol.38, p.605; Journal of the American Chemical Society, 1952, Vol. 74, p. 676; Journal Of the Americzn Chemical Society, 1964, Vol.86. p. 1839).

Further it is possible to carry out the above reaction using a condensing agent such as, for example, N,N'-dicyclohexylcarbodiimide, carbonyldiimidazole etc.

The above reaction can be carried out in about the th reaction, for example hydrocarbons, such as pentane, hexane, heptane, cyclohexane, petroleum ether, ligroin, benzene, toluene, xylene, etc., halogenated hydrocarbons such as dichloromethane, dichloroethane, chloroform, chetyrehhloristy carbon, chlorobenzene, dichlorobenzene, etc., ethers such as diethyl ether, di-ISO-propyl ether, dimethyl ether of ethylene glycol, tetrahydrofuran, dioxane, etc., ketones such as acetone, methyl ethyl ketone, methyl-ISO-propylketone, etc., acetates such as methyl acetate, the ethyl acetate, etc., NITRILES such as acetonitrile, propionitrile, benzonitrile, etc., aprotic solvents such as dimethylsulfoxide, dimethylformamide, sulfuron, etc. and a mixture solvent composed of a solvent selected from the already listed above.

May be the basis of any type commonly used in such reactions. You can, for example, hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide, etc., hydroxides of alkaline earth metals such as calcium hydroxide, etc., carbonates of alkali metals such as sodium carbonate, etc., organic bases such as triethylamine, triethylamine, dimethylaniline, pyridine, N-methylpiperidine, 1,5-Diaz is ethylamin, pyridine, N-methylpiperidin etc.

As a catalyst can be used 4-dimethylaminopyridine, 1-hydroxybenzotriazole, dimethylformamide, etc., the above reaction can be conducted at temperatures from -75oC to 100oC, preferably from -60o40oC. the Preferred time of reaction is 1-20 hours

Compounds represented by formula II and selected as starting materials are known and can be generally synthesized by known methods (see, for example, Methods der Organischen Chemie, Vol.15, No.2, p.2; Georg Thieme, Verlag Stuttgart: 1974, Chemistry of AminoAcids, vol.2, p.891: John Wiley Sons, N. Y. 1964; Journal of the American Chemical Society, 1957, Vol. 79, p.4686). Can be also considered many ways to obtain compound III (for example, Japanese patent application Sho 63-146876; Synthesis, 1978, p. 24). Most of the compounds of formula III are new connections.

The method of obtaining B

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where R1, R2, R3, R4, R5, R6, W, and Z represent the same as above; Y is a halogen atom, a group R, OC(O)O - or a group R C(O)O-.

Compounds according to the invention, represented by formula I, can be obtained by the interaction of the compounds represented by formula IV with amines, p is p. or salt derived amine with an organic acid, such as tosylate, etc. in the presence of a base, if necessary.

The above reaction can be carried out in conventional solvents, these solvents may be any solvent that does not inhibit the reaction, for example, hydrocarbons, such as pentane, hexane, heptane, cyclohexane, petroleum ether, ligroin, benzene, toluene, xylene, etc., halogenated hydrocarbons such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride, chlorobenzene, dichlorobenzene, etc., ethers such as diethyl ether, di-ISO-propyl ether, dimethyl ether of ethylene glycol, tetrahydrofuran, dioxane, etc., ketones, such as acetone, methyl ethyl ketone, methyl-ISO-propylketone, methyl-ISO-butylketone, etc., acetates such as methyl acetate, ethyl acetate, etc., NITRILES such as acetonitrile, propionitrile, benzonitrile, etc., aprotic solvents such as dimethylsulfoxide, dimethylformamide, sulfuron, etc. and a mixture solvent composed of a solvent selected from the already listed above.

May be the basis of any type commonly used in such reactions. You can, for example, be mentioned hydroxid, such as calcium hydroxide, etc., carbonates of alkali metals such as sodium carbonate, etc., organic bases such as triethylamine, trimethylamine, dimethylaniline, pyridine, N-methylpiperidine, 1,5-diazabicyclo[4.3.0] non-5-ene (DBN), 1,8-diazabicyclo[4.5.0]undec-7-ene (DBU), etc., preferably tertiary amines, such as triethylamine, pyridine, N-methylpiperidine, etc. Specified reaction can be conducted at temperatures from -20oC to 100oC, preferably from 0oC to 40oC. the Preferred time of reaction is from 30 minutes to 20 hours

Compounds represented by formula V and selected as starting materials are new materials and can be obtained, for example, processing of carbamates of compounds of formula I synthesized according to the method, presents the process of obtaining And using conventional methods of removal aminosidine groups of amino acids, such as catalytic reduction or by treatment with acids, such as liquid hydrofluoric acid, sulfonic acid, hydrochloric acid, Hydrobromic acid, formic acid, etc.

Below as reference examples of the synthesis of condensed GE is s for the compounds according to the invention.

Referential example 1. Synthesis of 1-[2-(5-nitrobenzofurazan)] ethylamine (intermediate compound 1).

37 g of ammonium acetate and 2.1 g of cyanoborohydride sodium is added to a solution containing 10 g of 2-(5-nitrobenzofurazan)ketone, dissolved in 500 ml of methanol, and the mixture was stirred for 30 min at room temperature. The reaction mixture is evaporated under reduced pressure and acidified with concentrated hydrochloric acid. To the mixture was added 300 ml of ethyl ether and 200 ml of water. After that, the resulting aqueous layer was alkalinized 5 th water solution of sodium hydroxide, the organic layer is extracted with 300 ml of ethyl ether, and then washed with water. The organic layer is dried over anhydrous sodium sulfate and the ether removed under reduced pressure with the formation of 4.0 g of the desired product as a light brown granular crystals (so pl. 53-59oC).

Referential example 2. Synthesis of 1-(6-chloro-2-benzo[in] thienyl)ethylamine (intermediate compound 2).

2.2 g of the hydrochloride of O-methylhydroxylamine and 1.3 g of potassium acetate is added to a solution containing 2.8 g of 2-acetyl-6-chlorobenzo[b]thiophene dissolved in 50 ml of methanol, and the resulting mixture is stirred at the boil with the reverse was built in what lacerata, washed successively with 5-Noah hydrochloric acid, 5% aqueous sodium bicarbonate solution and water, dried over anhydrous magnesium sulfate and evaporated.

Then 2.7 g of the obtained crude 6-chloro-2-(1-methoxyaminomethyl)benzo[b]thiophene was dissolved in 10 ml of dimethoxyethane and the resulting solution was added dropwise at room temperature to a suspension of 0.85 g of sodium borohydride in 20 ml of dimethoxyethane. After stirring for 5 min at the same temperature, to the mixture are added dropwise at room temperature a solution containing 4.26 deaths g of a complex of boron TRIFLUORIDE-diethyl ether in 5 ml of dimethoxyethane. After stirring for 30 min at the same temperature, the mixture is additionally stirred at the boil under reflux for 12 hours Then allow the mixture to cool to room temperature, then add 10-percent hydrochloric acid, bringing the pH of the mixture to the 3-4. Dimethoxyethane layer evaporated and combined with the aqueous layer and the pH increased to 7-8 with sodium carbonate. Extracted with dichloromethane and the dichloromethane layer is then washed, dried over anhydrous magnesium sulfate, filtered through Florisil and evaporated with the formation of 0.35 g of the target product is a transparent viscous liquid (figure Prel the x formula III and received on operations specified in reference examples 1 and 2, are given in table. 8.

Reference example 3. Synthesis of 1-[2-(5-cyano-2,3-dihydrobenzofuranyl)]ethylamine (intermediate compound 21).

4.0 g of ammonium acetate and 0.24 g of cyanoborohydride sodium is added to a solution containing 1.0 g of 2-(5-cyano-2,3-dihydrobenzofuranyl)of the ketone obtained by a known method (Org. Prep. Proced. Int. 4, 265 (1072)) in 50 ml of methanol, and the mixture was stirred for 30 min at room temperature. The reaction mixture is then evaporated under reduced pressure and acidified with concentrated hydrochloric acid. To the mixture was added 100 ml of ethyl ether and 50 ml of water. After that, the resulting aqueous layer was alkalinized 5 th water solution of sodium hydroxide. The organic layer is extracted and dried on anhydrous sodium sulfate. The ether is then removed under reduced pressure with the formation of 0.6 g of the desired product as a pale yellow oily substance (refractive index n2D01,5719).

Specific examples of the intermediate compounds represented by formula III obtained by the operations specified in reference example 3, are shown in table. 9.

Reference example 4. Synthesis of 1-[2-(5-chlorobenzophenone the Ute with stirring to 10 ml of 20 aqueous solution of methylamine in methanol, and then in small portions was added 0.8 g of sodium borohydride. To the resulting solution was added 2.8 g of 2-(5-chlorobenzophenone)ethylketone and the mixture is stirred at room temperature for 20 minutes the Reaction mass is then acidified with 10-Noah hydrochloric acid and the methanol removed under reduced pressure. The remaining aqueous solution was washed with chloroform and alkalinized with an aqueous solution of sodium hydroxide. The organic layer is then extracted with 200 ml of chloroform, washed and dried over anhydrous magnesium sulfate. Thereafter, the chloroform is removed under reduced pressure and the gain of 1.9 g of the desired product as a pale yellow oily substance (refractive index n2D01,5681).

Reference example 5. Synthesis of hydrochloride of N1-[1-(5-nitro-2-benzofuranyl)ethyl]-L-valinamide (intermediate compound 26).

5.0 g of N2-tert-butoxycarbonyl-N1-[1-(5-nitro-2-benzofuranyl)ethyl] -L - valinamide dissolved in 100 ml of tetrahydrofuran and placed for 1 h in a current of gaseous hydrogen chloride at room temperature. The reaction mass is then evaporated under reduced pressure and the resulting residue the crude product in the form of crystals washed with acetone. The yield of the target productone compound 27).

11.3 g of N2-tert-butoxycarbonyl-N1-[1-(2-benzo[b]thienyl)ethyl]-L-valinamide dissolved in 150 ml of ethyl acetate, after which the resulting solution at room temperature was added 20 ml of 6 N. hydrochloric acid. Leave overnight at room temperature and under stirring and cooling water to bring the pH to 7-8 with saturated aqueous sodium bicarbonate solution. The layer of ethyl acetate then washed, dried over anhydrous magnesium sulfate and evaporated, to give crude product. This crude product is further purified column chromatography on Florisil and allocate 6.7 g of the desired product as a white crystalline substance (so pl. 70-71oC).

Specific examples of the intermediate compounds represented by formula V obtained by the operations specified in reference examples 5 and 6, are given in table. 10.

Methods for producing compounds according to the invention and their use will be described in detail in the following examples.

Example 1. Synthesis of N2-tert-butoxycarbonyl-N1-[1-(5-cyano-2-benzofuranyl)ethyl]-L - valinamide (compound 16).

0.4 g of N-methylpiperidine at a temperature of not higher than -20oC is added to the solution containing 0.8 g of N-tert-butoxycarbonyl-the Ute thereto 0.5 g of ISO-butylchloroformate and stirred at a temperature of from -40oC to -15oC for 1 h To the mixture at -20oC is added 0.7 g of 1-(5-cyano-2-benzofuranyl)ethylamine and with stirring, allow it to warm to room temperature. Then added to the reaction mixture water. The dichloromethane layer is washed successively with 5-s ' solution of sodium bicarbonate and water, dried over anhydrous magnesium sulfate and evaporated. The remainder, which is a crystalline substance, clear column chromatography on silica gel, gaining 0.7 g of the desired product as a white powder.

Example 2. Synthesis of N1-[1-(5-chloro-2-benzofuranyl)ethyl] -N2-ISO-propoxycarbonyl-L - valinamide (Connection N 70, 71 and 296)

At -15oC gain of 0.54 g of N-methylmorpholine, and then 0.7 g ISO-propylchloride to a solution containing of 1.57 g of the hydrochloride of N-[1-(5-chloro-2-benzofuranyl)ethyl] -2-amino-3-methylbutylamine in 40 ml of dichloromethane. The obtained mixture is allowed to warm to room temperature and stirred at room temperature for 15 hours then added to the reaction mixture water. The dichloromethane layer is washed with water, dried over anhydrous magnesium sulfate and then evaporated. The remainder, which is a crystalline substance, the x2">

0.8 g of the mixture of diastereoisomers obtained in the reaction described above, separated using liquid chromatography. Ingredient which eluted first, evaporated, gaining 0.4 g of the target diastereoisomer in the form of a white powder.

Example 3. Synthesis of N2-ISO-propoxycarbonyl-N1-[1-(5-nitro-2-benzofuranyl)ethyl]-L - valinamide (compound 108).

At -15oC added 0.17 g of N-methylmorpholine, and then 0.18 g ISO-propylchloride to a solution containing 0.5 g of N-[1-(5-nitro-2-benzofuranyl)ethyl] -2-amino-3-methylbutylamine in 40 ml of dichloromethane. The obtained mixture is allowed to warm to room temperature and stirred at room temperature for 15 hours then added to the reaction mixture water. The dichloromethane layer is washed with water, dried over anhydrous magnesium sulfate and then evaporated. The remainder, which is a crystalline substance, clear column chromatography on silica gel, receiving 0.1 g of the target product as a white powder.

Example 4. Synthesis of N1-[1-(6-fluoro-2-benzofuranyl)ethyl] -N2-ISO-propoxycarbonyl-L-valinamide (compound 115).

4.7 g of N-methylpiperidine at -20oC is added to the solution containing the 9.7 gin. Then, at -30oC added thereto 6.5 g ISO-butylchloroformate and the resulting mass is stirred at a temperature of from -30oC to -20oC for 30 minutes To the mixture at -50oC is added to 8.5 g of 1-(5-fluoro-2-benzofuranyl)ethylamine and with stirring, allow it to warm to room temperature, and then stirred at room temperature for 15 hours then added to the reaction mixture water. The dichloromethane layer is washed with water, the organic layer is dried over anhydrous magnesium sulfate and evaporated. The remainder, which is a crystalline substance, clear column chromatography on silica gel, receiving 10.6 g of the desired product as a white powder.

Example 5. Synthesis of 2-tert-butoxycarbonyl-N-[1-(5-chloro-2-benzofuranyl)ethyl]-2,3-dimethylbutyramide (compound 140).

of 2.6 ml of 1 M aqueous solution of sodium bicarbonate and 0.62 g of di-tert-BUTYLCARBAMATE added at 0oC to stir the solution containing 0.8 g of 2-amino-N-[1-(5-chloro-2-benzofuranyl)ethyl] -2,3-dimethylbutyramide in 15 ml of solvent. The mixture is stirred at room temperature for 30 min, and then evaporated. The residue is extracted with ethyl acetate and the organic layer washed with water, dried over Sul is afia on silica gel, getting 0.52 g of the desired product as a white powder.

Example 6. Synthesis of N1-[1-(5-chloro-2-benzofuranyl)ethyl]-N2-(N-methylanilinium)-L-valinamide (compound 151).

At -15oC added sequentially 0.34 g of N-methylmorpholine and 0.57 g of N-methyl-N-phenylcarbamoyl to a solution containing 1.1 g of the hydrochloride of N-[1-(5-chloro-2-benzofuranyl)ethyl] -2-amino-3-methylbutylamine in 30 ml of dichloromethane. The obtained mixture is allowed to warm to room temperature and stirred at room temperature for 15 hours then added to the reaction mixture water. The dichloromethane layer is washed with water, dried over anhydrous magnesium sulfate and then evaporated. The remainder, which is a crystalline substance, clear column chromatography on silica gel, obtaining 1.1 g of the desired product as a white powder.

Example 7. Synthesis of N2-tert-butoxycarbonyl-N1-{1-[3-methyl-2-benzo[b]thienyl]ethyl}-L - valinamide (compound 159).

0.5 g of N-methylpiperidine at a temperature of not higher than -20oC is added to a solution containing 13 g of N-tert-butoxycarbonyl-L-valine in 25 ml of dichloromethane. Stirred the mixture at the same temperature for 10 min, then at -40ooC was added 1.0 g of 1-[3-methyl-2-benzo[b]thienyl]ethylamine and with stirring, allow it to warm to room temperature. Then added to the reaction mixture water. The dichloromethane layer was washed with successive 5-s ' solution of sodium bicarbonate and water, dried over anhydrous magnesium sulfate and evaporated the Residue, which is a crystalline substance, clear column chromatography on silica gel, obtaining 0.8 g of the desired product as a white powder.

Example 8. Synthesis of N1-[1-(5-toranzo[b]thiophene-2-yl)ethyl]-N2-ISO-propoxycarbonyl-L - valinamide (compound 192).

to 5.1 g of N-methylpiperidine at -20oC is added to the solution containing 10.4 g of N-ISO-propoxycarbonyl-L-valine in 200 ml of dichloromethane, and then to the resulting mixture are added dropwise 7.0 g ISO-butylchloroformate. The resulting mass is stirred at -20oC for 10 min and at -50oC added thereto 10.0 g of 1-(5-toranzo[b]thiophene-2-yl)ethylamine. Allow the mixture to warm to room temperature, and then stirred at room temperature for 15 hours After the reaction mixture was sequentially washed with 10% hydrochloric acid solution, n is involve. The residue is purified column chromatography on silica gel, receiving 12.3 g of the desired product as a white powder.

Example 9. Synthesis of N2-tert-butoxycarbonyl-N1-[1-(3-methyl-2-indolyl)ethyl] -L-valinamide (compound 240).

2.4 g N-methylpiperidine at a temperature of not higher than -20oC is added to the solution containing 3.1 g of N-tert-butoxycarbonyl-L-valine in 80 ml dichloromethane and stirred the mixture at the same temperature for 10 minutes At -40oC add to it 2.0 g ISO-butylchloroformate and stirred at a temperature of from -40oC to-15oC for 1 h To the mixture at -20oC add 2.5 g of 1-(3-methyl-2-indolyl)ethylamine and with stirring, allow it to warm to room temperature. Then added to the reaction mixture water. The dichloromethane layer is washed successively with 5-s ' solution of sodium bicarbonate and water, dried over anhydrous magnesium sulfate and evaporated. The residue is purified column chromatography on silica gel, obtaining 2.5 g of the desired product as a white powder.

Example 10. Synthesis of N2-tert-butoxycarbonyl-N1-[1-(2,3-dihydro-2-benzofuranyl)ethyl]-L-valinamide (compound 387).

of 0.37 g of N-methylpiperidine when the temperature of the stirred mixture at the same temperature for 10 minutes At -40oC add to her 0.51 g ISO-butylchloroformate and stirred at a temperature of from -40oC to -15oC for 1 h To the mixture at -20oC add 0.6 g of 1-(2,3-dihydro-2-benzofuranyl)ethylamine and with stirring, allow it to warm to room temperature. Then added to the reaction mixture water. The dichloromethane layer is washed successively with 5-s ' solution of sodium bicarbonate and water, dried over anhydrous magnesium sulfate and evaporated. The remainder, which is a crystalline substance, clear column chromatography on silica gel, receiving 0.5 g of the target product as a white powder.

Example 11. Synthesis of N2-tert-butoxycarbonyl-N1-[1-(3-indolyl)ethyl]-L-valinamide (compound 405).

0.7 g N-methylpiperidine at a temperature of not higher than -20oC is added to a solution containing 1.5 g of N-tert-butoxycarbonyl-L-valine in 50 ml of dichloromethane and stirred the mixture at the same temperature for 10 minutes At -40oC added thereto 0.9 g ISO-butylchloroformate and stirred at a temperature of from -40oC to -15oC for 1 h To the mixture at -20oC added 1.1 g of 1-(3-indolyl)ethylamine and under stirring to give her nagrela to the reaction mixture water. The dichloromethane layer is washed successively with 5-s ' solution of sodium bicarbonate and water, dried over anhydrous magnesium sulfate and evaporated. The remainder, which is a crystalline substance, clear column chromatography on silica gel, gaining 0.4 g of the desired product as a white powder.

Agricultural or horticultural fungicide according to the invention is a composition containing as active ingredient a condensed heterocyclic derivative represented by the formula I. In the case of the compounds according to the invention are used as agricultural and horticultural fungicides, compounds that act as active ingredients, can be depending on the destination obtained accordingly. The active ingredient is usually diluted in an inert liquid or solid carrier and, if necessary, add thereto a surfactant, a dispersant, a drug that enhances the action of the basic reagent, etc., Then cook the mixture in the usual manner, for example in the form of fine powder, wettable powder, capable of emulgirovanija concentrate, granules, etc.

Suitable examples of the wear is, kaolin, Demidova earth, vermiculite, white carbon black, slaked lime, silica sand, ammonium sulfate, urea, etc., or such liquid carriers, as ISO-propyl alcohol, xylene, cyclohexanone, methylnaphthalene, etc., Illustrative examples of surfactants and dispersants are salts dinaftiletilena acid, alkylarylsulfonates acid, ligninsulfonate acid, sulfate esters of an alcohol, esters of polyoxyethyleneglycol, polyoxyethylene ester alkylaryl, monoalkylated of polyoxyethylenesorbitan, etc., Suitable examples of the auxiliary agents are carboxymethyl cellulose, etc., These compositions can be used directly or after dilution to the desired concentration.

Agricultural or horticultural fungicides according to the invention can be used for different purposes, for example for seed treatment, for spraying the stems and leaves, to be added to the irrigation water to be added to the soil. Selects the desired proportion of the active ingredient. When the formulation is in the form of fine powder or granules, it is preferable to use 0.1 to 20 wt. the active ingredient. For mulgirigala concentrates or spaciotempo or horticultural fungicide according to the invention may vary depending on the type of the active component, the type of pest or disease which must be controlled, causes of the pest or disease, extent of injury, environmental conditions, forms of used drug, etc., In that case, if the agricultural or horticultural fungicide according to the invention are used directly in the form of fine powder or granules of the recommended rate of application of active ingredient must be appropriately selected in the range of from 0.1 g to 5 kg per 10 ar, preferably in the range from 1 g to 1 kg per 10 ar. Further, in those cases, if the agricultural or horticultural fungicide according to the invention is used in the form of a liquid, for example mulgirigala concentrate or wettable powder, the recommended rate of application of active ingredient must be appropriately selected in the range of 0.1 to 10000 hours per million), preferably in the range of 10-3000 hours/million

Compounds according to the invention in the form of the compositions described above can be used to control plant diseases caused by fungi belonging to Oomycetes, Ascomycetes, Deuteromycetes, Basidiomysetes or other pathogenic fungi. These fungi include, among others, Pseudoperonosopra, such as powdery mildew of cucumber (Pseudoperonospora cubensis), Phytophthora, such as late blight t the annual fungicides according to the invention can be used alone or in combination with other fungicides, insecticides, herbicides, modifiers plant growth, fertilizers, etc.

Typical compositions are given in the examples below recipes.

Example formulation 1. A fine powder.

2 wt. soedineniya 59, 5 wt. hard-shelled land and 93 wt. clay mix until smooth and fray in the dust.

An example of the formulation 2. Wettable powder.

50 wt. connection 70, 45 wt. hard-shelled land, 2 wt. dinaftiletilena sodium and 3 wt. lignosulfate sodium mix until smooth and fray in wettable powder.

Example formulation 3. Emulgirujushchie concentrate.

30 wt. compounds 5, 20 wt. cyclohexanone, 11 wt. polyoxyethylene ether arylalkyl, 4 wt. the Las calcium and 35 wt. methylnaphthalene dissolve with the formation of a homogeneous liquid, thus obtaining emulgirujushchie concentrate.

Example of formulation 4. Granules.

5 wt. compounds 16, 2 wt. laurylsulphate sodium, 5 wt. ligninsulfonate sodium, 2 wt. carboxymethylcellulose and 86 wt. clay mix and pound. 100 wt. PM received grinded mixture is added to 20 wt.h. water. The resulting mixture plastificated and Pribram what has been created granules.

The effectiveness of the invention.

Agricultural or horticultural fungicides according to the invention have a high ability to control the growth and spread of powdery mildew of cucumber (Pseudoperonospora cubensis), Phytophthora tomato (Phytophthora infestans) and downy mildew of grape (Plasmopara viticola). Further, the agricultural or horticultural fungicides according to the invention have not only the ability to control fungal infection, but have the ability to remove pathogenic fungi after they smote the host-plant. Moreover, the agricultural or horticultural fungicides according to the invention are characterized in that they are not harmful chemicals and have excellent characteristics, such as transitivity, long-term activity and resistance to the action of rain.

The effectiveness of the compounds according to the invention is illustrated further by the following examples testing.

Example test 1. Test the effectiveness of the protection against infection of powdery mildew of cucumber (Pseudoperonospora cubensis).

Seeds of cucumber (variety "Sagami hanjiro") are put in square pots are made from polyvinyl chloride with a side of 9 cm in the amount of 10 seeds per pot. Seeds germinated in the greenhouse for 7 dnei active ingredient 500 hours/million and the resulting aqueous drug treated cucumber seedlings at the stage of cotyledon with a rate of 10 ml per pot. After drying in the air to infect plants with a suspension of spores of the fungus powdery mildew of cucumber (Pseudoperonospora cubensis) and placed for 24 h in a moist chamber at 22oC. On the seventh day after infection to determine the amount of destruction in accordance with the conditional estimates in order to evaluate the protective effect of the compounds according to the invention. The results of the tests are shown in table. 11.

Contingent valuation:

Class a: Lesions not observed.

Class B: the Affected area is less than 25

Class C: the Affected area is more than 25 but less than 50

Class D: the Affected area is over 50

As a control were tested N2-(tert-butoxycarbonyl)-N1-(3-pyridylmethyl)-L-valinamide (comparative compound a, hereinafter referred to as "SA") and N2(phenoxycarbonyl)-N1-[1-(2-furyl)ethyl]-L-valinamide (comparative compound, hereinafter referred to as SV), which are described as active ingredients of fungicides (see Japanese patent application N 3-5451 and Japanese patent application N 3-153657). Recipe for tests using the specified compare the Test on the effectiveness of treatment for infections of powdery mildew of cucumber (Pseudoperonospora cubensis).

Seeds of cucumber (variety "Sagami hanjiro") are put in square pots are made from polyvinyl chloride with a side of 9 cm in the amount of 10 seeds per pot. Seeds germinated in the greenhouse for 7 days prior to the stage of cotyledon. Wettable powder obtained in example formulation 2, dilute with water to the concentration of the active ingredient 500 hours/million and the resulting aqueous drug treated cucumber seedlings at the stage of cotyledon with a rate of 10 ml per pot. After drying in the air to infect plants with a suspension of spores of the fungus powdery mildew of cucumber (Pseudoperonospora cubensis) and placed for 24 h in a moist chamber at 22oC. On the seventh day after infection to determine the amount of destruction in accordance with the conventional levels in order to evaluate the protective effect of the compounds according to the invention. Used the same comparative connections, as in the example test 1. The results of the tests are shown in table. 12.

Contingent valuation:

Class a: Lesions not observed.

Class B: the Affected area is less than 25

Class C: the Affected area is more than 25 but less than 50

Class D: the Affected area is over 50

Example of test 3. Test the effectiveness of protection inficiency pot (diameter 9 cm) and grown in the greenhouse. Wettable powder obtained in example formulation 2, dilute with water to the concentration of the active ingredient 500 hours/million and the resulting aqueous drug treated tomato seedlings at the stage of the 6-th or 7-th sheet at a rate of 20 ml per pot. After drying in air plants infect suspension zoosporangium inside host of the fungus Phytophthora tomato (Phytophthora infestans) and placed in a moist chamber at 22oC. On the fourth day after infection to determine the number of infected leaves. The prevalence of disease and the ability of the drug to protect against it is evaluated according to the following standards. The results of the tests are shown in table. 13. Used the same comparative compounds (CA and CB), as in the example test 1.

Standards test:

Index of infection 0: Lesions not observed.

Index 1 infection: the Affected area is less than 5

Index of infection 2: the Affected area is more than 5 but less than 33.3

Index of infection 3: the Affected area is more than 33,3 but less 66,6

Index of infection 4: the Affected area is more 66,6

< / BR>
Example of test 4. Test the effectiveness of protection infektsiija in ceramic pot (diameter 9 cm) and grown in the greenhouse. Wettable powder obtained in example formulation 2, dilute with water to the concentration of the active ingredient 500 ppm and the resulting aqueous drug treated seedlings of grapes in stage 4-th or 5-th sheet at a rate of 20 ml per pot. After drying in air, the plant infect suspension zoosporangium inside host fungus mildew of grape (Plasmopara viticola) and placed for 24 h in a moist chamber at 22oC. On the seventh day stay in the greenhouse after infection the plant again for 24 h, placed in a humid chamber at a temperature of 22oC for cultivation conidiospore. Infected areas on each sheet, on which grew conidiospore, inspect in accordance with the following standards. The prevalence of disease and the ability of the drug to protect her appreciate in the same way as described in example test 3. The results of the tests are shown in table. 14. Used the same comparative connections, as in the example test 1.

Standards test:

Index of infection 0: Lesions not observed.

Index 1 infection: the Affected area is less than 5

Index of infection 2: the Affected area is not more than 5 but less than 33.3

Index inficirovannye more 66,6

1. Condensed heterocyclic derivatives of General formula

< / BR>
where R' represents a C1C6is an alkyl group, optionally substituted by halogen atom, cyano or methoxy group, a C2C6-alkenylphenol group, C2C6-alkylamino group, C3C6-cycloalkyl group, C7- C10-aracelio group, optionally substituted by methyl or nitro-group, phenyl group, optionally substituted by a halogen atom, methyl, methoxy or nitro - group, dimethylaminopropyl, ethoxycarbonyl group or a C2C6cyclic ether;

R2hydrogen or a methyl group;

R3hydrogen, C1C6is an alkyl group, a C3- C6-cycloalkyl group, phenyl group, halogenoalkane group or kalkilya group, and R2with R3may form a cyclic ring;

R4hydrogen, C1C6is an alkyl group, or cyano;

R5hydrogen or a methyl group;

R6hydrogen or C1C6is an alkyl group;

Z is represented by the following formula:

< / BR>
< / BR>
< / BR>
< / BR>
where XIhydrogen, halogen, C1C9-alkylene is, is ethylthio-, methylsulfinyl, methylsulfonyl or the nitro-group;

n is 1 or 2;

XIIhydrogen, halogen, C1C6-alkyl, methoxy or nitro - group;

m is 1 or 2;

XIIIhydrogen, halogen, C1C6-alkyl or methoxy group;

XIVhydrogen, C1C6is an alkyl group, halogen or cyano;

R7hydrogen or a methyl group;

R8hydrogen or a methyl group;

W C(O)-, -SO2-, -NHC(O)- N(CH3)C(O)-, OC(O)-, OC(S)-, -SC(S)-, or-SC(O)-.

2. Derived under item 1, where R1C2C6is an alkyl group with straight or branched chain, C3-Alchemilla group with a straight or branched chain, C5C6-cycloalkyl group or phenyl group;

R2hydrogen;

R3ethyl, ISO-propyl or sec-bucilina group;

R4hydrogen, methyl or ethyl group;

R5hydrogen or a methyl group;

R6hydrogen;

Z compounds having the following formula:

< / BR>
< / BR>
where XIfluorine, chlorine, methyl, cyano - or nitro-group;

n is 1 or 2;

XIIfluorine, chlorine, methyl or nitro-group;

m is 1 or 2;

XIIIfluorine, chlorine or methyl/BR> W-OC(O)-,

and the amino acid is an L-isomer.

3. Derived under item 1, where R1ISO-propyl, tert-bucilina, second-bucilina, cyclopentamine, isopropylene or phenyl group, R2hydrogen, R3ethyl, ISO-propyl or sec-bucilina group, R4methyl group, R5hydrogen, R6is hydrogen, Z is represented by the following formula:

< / BR>
where XIfluorine, chlorine, methyl, cyano - or nitro-group;

n is 1 or 2;

XIIfluorine, chlorine, methyl or nitro-group;

m is 1 or 2;

W-OC(O)-,

and the amino acid is an L-isomer.

4. Derived under item 1, in which the derivative is N'-[1-(5-chloro-2-benzofuranyl)ethyl] -N2-cyclopentanecarbonyl-L-valinamide, N'-[1-(5-chloro-2-benzofuranyl)ethyl] -N2-isopropoxycarbonyl-L-valinamide, N'-[1-(5-fluoro-2-benzofuranyl)ethyl] -N2-isopropoxycarbonyl-L - valinamide, N2-isopropoxycarbonyl-N'-[1-(5-nitro-2 - benzofuranyl)ethyl] - L-valinamide, N'-/1-(5-fluoro-2-benzo/b/thienyl)-ethyl] -N2-isopropoxycarbonyl-L-valinamide, N'-[1-(6-fluoro-2-benzo/b/thienyl)ethyl] -N2-isopropoxycarbonyl-L-valinamide, N2-Deut-butyloxycarbonyl-N'-/1-(5-chloro-2-benzofuranyl)ethyl] -L - alinamin or N'-[1-(5-chloro-2-benzofuranyl) the CSO derivative of General formula

< / BR>
where R1R6, W and Z have values under item 1,

characterized in that the derived amino acid of General formula

< / BR>
where R1R3and W have the values under item 1,

or a derivative of the amino acid with the activated carboxyl group is subjected to interaction with equivalent or more amine derivative of General formula

< / BR>
where R4R6and Z have values under item 1.

6. A method of obtaining a condensed heterocyclic derivative of the General formula

< / BR>
where R1R6, W and Z have values under item 1,

characterized in that the amine derivative of General formula

< / BR>
where R2R6and Z have values under item 1,

or salt of the amine derivative with an organic or inorganic acid, is subjected to the interaction with an equivalent or more compounds of General formula

R'-W-Y,

where R' and W are set to p. 1;

Y is halogen or a group R, OC(O)O-, or R C(O)O-

7. Agricultural fungicidal composition, comprising an active substance and additives target, characterized in that the active substance it contains a compound of formula I under item 1 in an effective amount.

8. The way of fighting is m, characterized in that the active ingredient is used as a compound of formula I under item 1, in the amount of 0.6 1.56 kg/ar for solid fungicide or 500 million-1for liquid fungicide.

9. Derived under item 1, where R1C1C6is an alkyl or phenyl group, optionally substituted by a halogen atom or a methyl group, R2hydrogen, R3C1C6is an alkyl group, R4C1C6is an alkyl group, R5is hydrogen, R6hydrogen, Z -

< / BR>
where XIhalogen, triptoreline or the nitro-group;

n 1;

W-OC(O)-.

10. Derived by p. 9, where R' is an alkyl group branched chain or a phenyl group, R2hydrogen, R3ISO-propyl group, R4methyl group, R5hydrogen, R6hydrogen, Z -

< / BR>
where XIfluorine, chlorine or nitro-group;

n 1;

W-OC(O)-,

and the amino acid is an L-isomer.

11. Derived by p. 9, where R' is tert-bucilina or phenyl group, R2hydrogen, R3ISO-propyl group, R4methyl group, R5hydrogen, R6hydrogen, Z -

< / BR>
where XIfluorine, chlorine or nitro-group, n is 1, W is-OC(O)-,

and the amino acid is an L-isomer.

13. Derived under item 1, where R1C1C6is an alkyl group, optionally substituted by a halogen atom or a methoxy group, a C2C6-Alchemilla, C2C6-Alchemilla, C3- C6-cycloalkyl, C7C10-kalkilya group, optionally substituted by methyl or nitro-group, phenyl group, optionally substituted by a halogen atom or methyl group, dimethylamino - or ethoxycarbonyl group, R2hydrogen or a methyl group, R3hydrogen, C1C6-alkyl, C3- C6-cycloalkyl, phenyl, halogenoalkane or kalkilya group, and R2together with R3may form a cyclic ring, R4C1C6is an alkyl group, R5hydrogen, R6hydrogen, Z

< / BR>
< / BR>
where XIhydrogen, halogen, C1C9-alkyl, methoxy, triptoreline-, methoxycarbonyl, amino, dimethylamino-, phenyl, cyano-, methylthio-, methylsulfinyl, methylsulfonyl group, or the nitro-group;

n is 1 or 2;

XIIhydrogen, halogen, C1C6is an alkyl or nitro-group;

m is 1 or 2;

XIIIhydrogen or C1C6is an alkyl group;

XI or-OC(O)-.

14. Derived by p. 13, where R1C2C6is an alkyl group with straight or branched chain, C3-Alchemilla group with a straight or branched chain, C5C6-cycloalkyl or phenyl group, R2hydrogen, R3ethyl, ISO-propyl or sec-bucilina group, R4methyl or ethyl group, R5is hydrogen, R6hydrogen, Z -

< / BR>
< / BR>
where XIchlorine, methyl, cyano - or nitro-group;

n is 1 or 2;

XIIchlorine, methyl or nitro-group;

m is 1 or 2;

XIIImethyl group;

R7hydrogen or a methyl group;

W-OC(O)-,

and the amino acid is an L-isomer.

15. Derived by p. 13,

where R1ISO-propyl, tert-bucilina, second-bucilina, cyclopentamine, isopropylene or phenyl group, R2hydrogen, R3ethyl, ISO-propyl or sec-bucilina group, R4is a methyl group, R5hydrogen, R6hydrogen, Z -

< / BR>
where XIchlorine, methyl, cyano - or nitro-group;

n is 1 or 2;

XIIchlorine, methyl or nitro-group;

m is 1 or 2;

W-OC(O)-,

and the amino acid is an L-isomer.

16. Derived under item 3, which is N-[ethyl]-N2-isopropoxycarbonyl-L-valinamide, N2-isopropoxycarbonyl-N'-[1-(5-nitro-2-benzofuranyl)-ethyl] -L-valinamide or N2-Deut-butyloxycarbonyl-N'-[1-(5-chloro-2-benzofuranyl)ethyl]-L-valinamide.

Priority points

30.07.93 on PP.1 4.

07.09.92 on PP.5 8.

07.09.92 on PP.9 to 12.

28.01.93 on PP.13 16.

 

Same patents:

The invention relates to new heterocyclic compounds, more specifically to new heterocyclic compounds, which are inhibitors of the enzyme 5-lipoxygenase (hereinafter referred to as 5-LO)

The invention relates to new agrochemical compounds, in particular derivatives valinamide General formula (I)

R1-O-CO-NH-R2where R1- ISO-propyl or sec.-butyl;

R2- chlorine, methyl, ethyl or methoxy-group in the form of a racemate or in R(+)-configuration L-isomer having fungicidal activity

FIELD: organic chemistry, agriculture, herbicide composition.

SUBSTANCE: invention relates to herbicide composition, containing conventional inert additives and mixture of a) herbicidically effective amount of substance satisfying the formula I [in formula R1 and R3 are the same or different C1-C4-alkyl; R4 and R5 together form groups of formulae: -C-R6(R7)-O-C-R8(R9)-C-R10(R11)-C-R12(R13)-(Z1), -C-R14(R15)-C-R16(R17)-O-C-R18(R19)-C-R20(R21)-(Z2), or -C-R22(R23)-C-R24(R25)-C-R26(R27)-O-C-R28(R29)-(Z3), wherein each R6-R29 is hydrogen; G is hydrogen or -C(X2)-X3-R31; X2 and X3 independently are oxygen; R31 is C1-C10-alkyl]; b) herbicidic synergic amount of at least one herbicide selected from group containing sulfonylureas, phenoxyacetic acids, as well as florsulam, tralcoxidim, klodinafol-propargil, phenoxaprop-P-ethyl, trifluramine, pendimethaline, picolinafen, etc. Composition also may contain safety effective amount of protective agent, such as chloquintocet-mexyl and additive (e.g., mineral oil or C8-C22-fat acid alkyl esters) in amount of 0-2 mass %. Also disclosed is method for selective controlling of weeds and grassy plants in cultural plants by treatment of cultural plants, seeds or seedlings thereof, or vegetation area thereof with claimed composition.

EFFECT: effective composition and method for weed controlling.

5 cl, 11 tbl, 7 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: agricultural chemistry.

SUBSTANCE: invention relates to herbicidal composition containing (A) mesotrion and (B) the second herbicide selected from amicarbazone, metribuzine, flumetsulfam, trifloxysulfuron, pyriphthalide, prosulfocarb or herbicidically active salts thereof in (A):(B) ratio from 32:1 to 1:3. Disclosed is method for controlling of undesired plants which includes application of herbicidically effective amount of said composition into locus with such plants.

EFFECT: composition of high herbicidal activity.

8 cl, 6 tbl

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: biochemistry, agriculture.

SUBSTANCE: claimed combinations contain compound of formula I and the second component selected from group including of penconazol, pyrqclostrobin, trifloxystrobin, famoxadon, zoxamide, benalaxyle, phosphorous acid, and copper hydroxide in synergetically effective ratio. Also described are fungicidal combinations containing compounds of formula Ia and the second component selected from abovementioned group.

EFFECT: synergetic fungicidal combinations with increased activity.

6 cl, 4 tbl, 2 ex

FIELD: agriculture.

SUBSTANCE: proposed synergetic effect herbicide compound contains efficient amounts of components (A) and (B), with (A) standing for a single or multiple herbicide substance(s) with general formula as well as salts thereof and (B) standing for a single or multiple herbicide substance(s) that are used for selective control of monocotyledonous and/or dicotyledonous weeds with monocotyledonous cultivated plants and belong to the compounds group including: (B1) flucarbazon, (B2) BAY MKH 6561 (procarbazon), (B3) florasulam, (B4) halosulphuron, (B5) tritosulphuron, (B6) pikolinafen, (B7) cinidon-ethyl, (B8) mezotrion, (B9) metosulam, (B10) cloryralid, (B11) flufenacet, (B12) flumetsulam, (B13) flupoxam, (B14) prosulphocarb, (B15) flutramon, (B16) aclonifen, (B17) hexazinon, (B18) asulam, (B19) diuron, (B20) amertin, (B21) izoxaflutol, (B22) amicarbazon, (B23) trifloxisulphuron; excluded are the herbicide compounds whose (A) component is one or several herbicide substances belonging to the (I) general formula group as well as salts thereof where R1 is (C1-C8)-alkyl, (C3-C4)-alkenyl or (C3-C4)-alkinyl, R2 is CH2NHSO2CH3, R3 is metoxi and Z is CH, and (B) component is one or several herbicide substances belonging to the compounds group including (B9), (B13), (B14) and (B15).

EFFECT: quantitative minimisation of specific agents application.

7 cl, 8 tbl, 4 ex

FIELD: agriculture.

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

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

2 cl, 9 tbl, 6 ex

FIELD: chemistry.

SUBSTANCE: description is given of a fungicide composition containing a) a pyridylethylenebenzamide derivative with general formula (I), where p equals 2, q equals 1, each substitute X is independently chosen and is a halogen, halogenalkyl, containing 1-5 carbon atoms, Y is a halogenalkyl, containing 1-5 carbon atoms, and b) a compound, capable of inhibiting spore germination or growth of micellium through effect on different metabolic routes, which is iprodione, captan, folpet, 2,6-dichloro-N-{[3-chloro-5-(trifluoromethyl)-2pyridinyl]}benzamide, benalaxyl, chlorothalonil, fludioxonil, mankozeb, metalaxyl-M, propamocarb, propineb, tolylfluanid, fosetyl-A1, with mass ratio (a)/(b) between 0.04 and 9. A method is also described for preventive or remedial control of phytopathogenic fungi in crops.

EFFECT: composition provides synergetic effect.

9 cl, 1 tbl, 1 ex

FIELD: medicine.

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

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

8 cl, 13 tbl, 12 ex

FIELD: medicine.

SUBSTANCE: there is described a herbicidal composition containing (a) prosulphocarb and (b) at least one compound chosen from the group including sulcotrion and pyrazolinate, where the mixing ratio of active ingredients (a) and (b) is 50:1 to 1:50. There are also described methods to control the ALS and ACCase resistant weeds in useful cropping.

EFFECT: composition is applicable for selective control of undesired vegetation, such as weeds (herb and broad-leaved weeds), in useful cropping, eg in rice, grain crop and corn.

6 cl, 14 tbl, 2 ex

FIELD: plant protection.

SUBSTANCE: invention provides fungicidal composition comprising aqueous solution of ferric sulfate (50%) and calcium hydroxide (20%) to produce neutral or low alkaline reaction of working fluid. Composition is further supplemented by urea as mineral fertilizer (30%). Ratio of total amount of components to water is (1-3):100 and pH of solution is 5.5-7.5.

EFFECT: enabled supplementary function of fungicide as extra-root additional fertilizing thereby favorably influencing growth and fructification of fruit plants.

2 cl, 5 tbl

FIELD: agriculture, in particular plant production.

SUBSTANCE: method of present invention includes utilization of urea hydroperoxide as nitrogenous fertilizer with nematocide and fungicide properties. Fertilizer of present invention also is useful in plant protection against diseases and blasts, such as potato-root eelworm and gall-root eelworm.

EFFECT: increased soil microbiological activity and fertility.

8 tbl, 8 ex

FIELD: agriculture, in particular fungicide composition.

SUBSTANCE: claimed composition contains (mass %) carbamide 0.5-3 and aqueous cupperas solution 0.5-3 in ratio of 1-2:1, wherein pH of working solution is 5.5-7.

EFFECT: composition useful not only as fungicide but also as plant growth and fruitage promoter due to nitrogen and iron content.

6 tbl

FIELD: agriculture.

SUBSTANCE: claimed composition contains (g/t): benzimidasole derivatives (e.g. agrocite, bendan, usgene, fundasol) as protectant not less than 300; and target additives: carbamide 20-25; potassium monosubstituted phosphate 9-12; potassium chloride 7-10; copper sulfate 120-125; zinc sulfate 120-125; magnesium sulfate 120-125; cobalt sulfate 10-12; manganese sulfate 15-17; ammonium molybdate 16-18; and water 1000-1050. Composition for seed pretreatment contains abovementioned components in the same ratio and water soluble film-forming agent in amount of 10-12 g/t.

EFFECT: decreased protectant consumption.

5 cl, 2 ex

FIELD: agriculture.

SUBSTANCE: claimed composition contains arachidonic acid and urea in ratio of 1:1-1:8 and additionally lower C1-C4-alkohol as solvent. More particularly composition contains (mg/1 ml of solvent): arachidonic acid 0.01-1.00 and urea 0.01-3.00. Moreover composition optionally contains ionol as antioxidant in ratio arachidonic acid/ionol of 1:1.

EFFECT: composition for plant treatment with improved effectiveness.

3 cl, 9 tbl, 7 ex

FIELD: agriculture.

SUBSTANCE: complex compound of carbamide with hydrogen peroxide containing 64.3% of urea, 35% of hydrogen peroxide, 0.15-0.25% of citric or oxalic acid and 0.5-5.0% of sodium tri polyphosphate as a plant growth regulator is applied.

EFFECT: increase of yield and resistance to diseases.

4 ex, 6 tbl

Herbicide compound // 2356228

FIELD: agriculture.

SUBSTANCE: compound contains triethanolamine, water, sulfonyl urea with the following mole ratio: 0.043:1:0.05 or 0.05:0.049:1 or 0.045:2:0.05 respectively.

EFFECT: enhancement of the compound stability.

11 ex, 2 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to agriculture. The method of stimulating growth of spring wheat involves seed treatment with 0.005% aqueous solution of a preparation of formula: H3BO3*4R1R2NC(S)NR3R4, where R1=R2=R3=R4=CH3 ("БТТМ"); R1=C6H5, R2=R3=H, R4=(CH2)3OH (BFPA); R1=o-CH3C6H4, R2=R3=H, R4=(CH2)3OH (BTPA), and vegetative plants are also sprayed with the same preparation during the tillering period at usage rate of 200 g/ha.

EFFECT: invention reduces spread of spot blight, increases plant survival rate and increases spring wheat yield.

5 tbl, 4 ex

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